TW201026877A - Method for depositing conformal amorphous carbon film by plasma-enhanced chemical vapor deposition (PECVD) - Google Patents

Method for depositing conformal amorphous carbon film by plasma-enhanced chemical vapor deposition (PECVD) Download PDF

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TW201026877A
TW201026877A TW098134833A TW98134833A TW201026877A TW 201026877 A TW201026877 A TW 201026877A TW 098134833 A TW098134833 A TW 098134833A TW 98134833 A TW98134833 A TW 98134833A TW 201026877 A TW201026877 A TW 201026877A
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amorphous carbon
gas
substrate
processing chamber
plasma
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TW098134833A
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Chinese (zh)
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TWI421364B (en
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Kwangduk Douglas Lee
Takashi Morii
Yoichi Suzuki
Sudha Rathi
Martin Jay Seamons
Deenesh Padhi
Bok Hoen Kim
Cynthia Pagdanganan
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Applied Materials Inc
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    • H—ELECTRICITY
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02115—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material being carbon, e.g. alpha-C, diamond or hydrogen doped carbon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
    • C23C16/509—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges using internal electrodes
    • C23C16/5096—Flat-bed apparatus
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02592—Microstructure amorphous
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/3141—Deposition using atomic layer deposition techniques [ALD]
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/3146—Carbon layers, e.g. diamond-like layers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

Methods and apparatus for depositing an amorphous carbon layer on a substrate are provided. In one embodiment, a deposition process includes positioning a substrate in a substrate processing chamber, introducing a hydrocarbon source having a carbon to hydrogen atom ratio of greater than 1: 2 into the processing chamber, introducing a plasma initiating gas selected from the group consisting of hydrogen, helium, argon, nitrogen, and combinations thereof into the processing chamber, with the hydrocarbon source having a volumetric flow rate to plasma initiating gas volumetric flow rate ratio of 1:2 or greater, generating a plasma in the processing chamber, and forming a conformal amorphous carbon layer on the substrate.

Description

201026877 六、發明說明： 【發明所屬之技術領域】 本發明實施例大體而言係有關於積體電路的製造，並 且更明確地說，係有關於在一半導體基材上沈積一無定 形碳層。 【先前技術】 φ 積體電路已演進為可容納數百萬個電晶體、電容器和 電阻器在單一個晶片上的複雜元件。晶片設計的進化持 續要求更快的電路及更大的電路密度。對於更快的電路 以及更大的電路密度之要求也對用來製造此類積體電路 的材料加諸相對應的要求。明確地說，隨著積體電路零 組件的尺寸縮小至次微米尺寸，不僅必須使用低電阻係 數的導電材料，例如銅，以改善元件的電氣效能，並且 參也必須使用低介電常數絕緣材料，常稱為低k介電材 料。低k介電材料一般具有低於38的介電常數。 製造具有低k介電材料以及極少或沒有表面缺陷或特 徵結構變形的元件是困難的。介電常數低於約3 〇的低k 介電材料常是多孔且容易在隨後的製程步驟期間到傷或 受損，因此增加缺陷形成在該基材表面上的可能性。此 類低k介電材料通常是易碎的且可能在習知研磨製程下 變形，例如化學機械研磨（CMP)。一種限制或減少此類 低k介電材料的表面缺陷及變形的解決方法是在圖案化 4 201026877 及蝕刻之前，先在暴露出的低k介電材料上沈積硬光 罩。該硬光罩避免脆弱的低k介電材料損壞及變形。此 外，硬光罩層結合習知微影技術可作用為钱刻光罩，以 避免低k介電材料在餘刻期間被除去。 此外，硬光罩幾乎在積體電路製造製程的每-個步驟 中使用’用於前端和後端製程兩者。隨著元件尺寸縮小 以及圖案結構日益複雜和難以製造，韻刻硬光罩更形重201026877 VI. Description of the Invention: [Technical Field of the Invention] Embodiments of the present invention generally relate to the fabrication of integrated circuits and, more particularly, to depositing an amorphous carbon layer on a semiconductor substrate. . [Prior Art] The φ integrated circuit has evolved into a complex component that can accommodate millions of transistors, capacitors, and resistors on a single wafer. The evolution of wafer design continues to require faster circuits and greater circuit density. The requirements for faster circuits and greater circuit density also place corresponding requirements on the materials used to fabricate such integrated circuits. Specifically, as the size of integrated circuit components shrinks to sub-micron size, it is necessary to use not only a low resistivity conductive material, such as copper, to improve the electrical performance of the component, but also a low dielectric constant insulating material. Often referred to as low-k dielectric materials. Low-k dielectric materials typically have a dielectric constant below 38. It is difficult to fabricate components having low-k dielectric materials with little or no surface defects or characteristic structural distortion. Low-k dielectric materials having a dielectric constant of less than about 3 Å are often porous and susceptible to damage or damage during subsequent processing steps, thereby increasing the likelihood that defects will form on the surface of the substrate. Such low-k dielectric materials are typically fragile and may be deformed under conventional polishing processes, such as chemical mechanical polishing (CMP). One solution to limit or reduce surface defects and distortion of such low-k dielectric materials is to deposit a hard mask on the exposed low-k dielectric material prior to patterning 4 201026877 and etching. The hard mask prevents damage and deformation of the fragile low-k dielectric material. In addition, the hard mask layer, in conjunction with conventional lithography, acts as a reticle to prevent the low-k dielectric material from being removed during the remainder. In addition, hard masks are used in almost every step of the integrated circuit fabrication process for both front-end and back-end processes. As the component size shrinks and the pattern structure becomes more complex and difficult to manufacture, the rhyme hard mask is more heavy.

要，因4現行《阻無法符合银刻抗性要纟，並且光阻僅 是用來進行影像轉移而非在微影和_製程中做為儀刻 光罩。反之，接收影像圖案的硬光罩日漸成為在下方層 中有效蝕刻圖案的首要材料。 無定形氫化碳是一種可用來做為金屬、無定形矽、以 及介電材料，例如二氧切錢切㈣，除了其他之 外’的硬光罩之材料。無定形氫化碳，也稱為無定形碳 並可表示為a_C:H或a_c:H’被視為是無長程結晶序的 碳材料，且可含有重要的氫含量，例如約i〇“5的氫 原子.百分比等級。已觀察到無定形碳擁有化學惰性、光 學透明性、以及良好的機械性fe雖然可用若干技術來 沈積a_C:H膜，但電衆增強化學氣相沈積（PECVD)因其 成本效益及薄膜性質可調性而廣為使用。在一典型 PECVD製程巾’-錢化合物來源，例如承載在一載氣 中的氣態碳氫化合物或液態碳氫化合物，係經通入一 PECVD腔室内。㈣在該腔室内起始電衆，以產生激發 的CH-自由基。該等激發的自由基化學性鍵結至設置在 5 201026877 該腔室内的t _ ^ 材之表面’在其上形成預期的a-C:H膜。 就=光罩層係'沈積在具有形貌特徵結冑的基材上之應 用β該硬光罩層必須共形覆蓋該形貌特徵結構的所 有表面此外’隨著特徵結構尺寸縮小，由於光波長和 圖案尺寸的限制’光阻材料難以正確轉移圖案。因此， 日漸需要新的製程和材料來滿足這些挑戰，其中硬光罩 件之關鍵尺寸的有效轉移變得不可或缺。 硬光罩層沈積共形性在具有下方形貌的基材上是很難實 現的’例如用來對準該圖案化製程的對準鍵。第1圖示 出具有特徵結構111及形成在其上之非共形無定形碳層 112的基材1〇〇之概要剖面圖。因為非共形無定形碳層 U2並非完全覆蓋特徵結構111的侧壁114,隨後的蝕刻 製程可能造成有害的側壁！ 14腐蝕。侧壁i 14由非共形 無定形碳層112完整覆蓋的缺乏也可能造成非共形碳層 112下方材料的光阻毒化，其已知會損傷電子元件。 φ 因此，存有對於一種可用於積體電路製造之可共形沈 積在具有形貌特徵結構的基材上之材料層的沈積方法之 需要。 【發明内容】 本發明實施例提供一種處理基材的方法，例如藉由在 該基材上沈積一無定形碳層。該方法，根據一第一實施 例’包含將一基材設置在一基材處理室内，將碳對氫原 6 201026877 子比大於1:2的一碳氫化合物來源通入該處理室，將選 自由氫氣、氦氣、氬氣、氮氣、及其組合物所組成的族 群之一電漿起始氣體通入該處理室，並且該碳氫化合物 來源的體積流速對該電漿起始氣體的體積流速比為1:2 或更大’在該處理室内以1瓦/平方公分或更低的rF 功率、2托耳或更高的壓力、以及約3〇〇〇c至約48〇。(：的 溫度產生一電漿，以及在該基材上形成一共形無定形碳 層。 在另一實施例中，提供一種處理一基材的方法，其包 含執行一沈積循環’包含在該基材的一表面上形成一共 形無定形碳材料，以及使一淨化氣體流動通過該處理 室’以及重複該循環2至50次之間。 在另一實施例中’提供一種處理一基材的方法，其包 含將一基材設置在一基材處理室内，將碳對氫原子比大 於1.2的一碳氫化合物來源通入該處理室，將選自由氫 Φ 氣、氦氣、氬氣、氮氣、及其組合物所組成的族群之一 電聚起始氣體通入該處理室，並且該碳氫化合物來源的 艘積流速對該電漿起始氣體的體積流速比為1:2或更 大’其中該碳氫化合物來源和該電漿起始氣體係利用設 置在距離基材表面400密爾和600密爾之間的一氣體分 配器通入該處理室，在該處理室内以1瓦/平方公分或 更低的RF功率以及約〇ec至約1 〇〇°c之間的溫度產生一 電漿’以及在該基材上形成一共形無定形碳層。 7 201026877 【實施方式】 在此所述實施例大體而言提供在一化學氣相沈積系統 内沈積具有改善的共形性之無定形碳材料（a_c.H)的方 法。一個層的共形性通常是用沈積在一特徵結構側壁上 之一層的平均厚度對相同沈積層在該基材範圍，或上表 面’上的平均厚度之比例（其可表示為百分比）來量化。 觀察到利用在此所述方法沈積的層具有大於約3〇%，例 φ 如70°/〇或更尚，約7 : 1〇或更大，例如約80。/。或更高， 約4 : 5或更大’至約100% ’約！ ： ！的共形性。例如， 會認定第1圖所示之先前技藝非共形無定形碳層112具 有〇%共形性，因為在侧壁丨14上缺乏層沈積。 明確地說，提供一改善的a_c:H層共形沈積之方法。 共形沈積可藉由使用碳對氫比例為1:2或更高的前驅 物，例如碳對氫比例為2: 3或更高，利用選自由氦氣、 氫氣、氮氣、氬氣、或其組合物所組成的族群之電漿起 • 始氣體’以增加的前驅物對電漿起始氣體流速，以增加 的沈積壓力，以增加的沈積溫度，以較低的rf功率應 用，利用具有降低的沈積速率之電漿環境，藉由在多個 層内沈積無定形碳，及其組合來改善。此間沈積製程可 在一適合的處理系統内執行。 第3圖係一基材處理系統’系統3〇〇，的概要示意圖， 其可用來進行根據本發明實施例之無定形碳層沈積。適 合系統的範例包含CENTURA®系統，其可使用DxZ™處 8 201026877 理室，PRECISION 5000®系統，PR〇DUCERTM系統例 如PRODUCER SE™處理室和pr〇ducer GTTM處理室 所有皆可由加州聖塔克拉拉的應用材料公司購得。 系統300包含製程腔室325、氣體分配盤33〇、控制單 元3 1 0、及其他硬體零組件，例如電源和真空幫浦。在 本發明中使用的系統之一實施例的細節在共同讓渡之 2002年4月2號核准之美國專利第6,364 954號之“出叻Yes, because the current "resistance can not meet the requirements of silver engraving resistance, and the photoresist is only used for image transfer rather than as an illuminating mask in lithography and process. Conversely, a hard mask that receives an image pattern increasingly becomes the primary material for effectively etching the pattern in the underlying layer. Amorphous hydrogenated carbon is a material that can be used as a hard mask for metals, amorphous germanium, and dielectric materials, such as dioxic cuts (iv), among others. Amorphous hydrogenated carbon, also known as amorphous carbon, and can be expressed as a_C:H or a_c:H' is considered to be a carbon material without a long-range crystal sequence, and may contain an important hydrogen content, for example, about 〇5 Hydrogen atom. Percentage grade. It has been observed that amorphous carbon possesses chemical inertness, optical transparency, and good mechanical properties. Although several techniques can be used to deposit a_C:H film, but electron enhanced chemical vapor deposition (PECVD) Cost-effective and film properties are widely used. In a typical PECVD process towel, a source of money, such as gaseous hydrocarbons or liquid hydrocarbons carried in a carrier gas, is passed into a PECVD chamber. Indoors. (iv) Initiating electricity in the chamber to generate excited CH-free radicals. The excited free radicals are chemically bonded to the surface of the t_^ material disposed in the chamber at 5 201026877 Forming the intended aC:H film. As applied to the application of the photomask layer on a substrate having a topographical feature, the hard mask layer must conformally cover all surfaces of the topographical feature. The feature structure is reduced in size due to Limitations of Wavelength and Pattern Size 'Photoresist materials are difficult to transfer patterns correctly. Therefore, new processes and materials are increasingly needed to meet these challenges, and the effective transfer of critical dimensions of hard mask parts becomes indispensable. Hard mask layer Deposition conformality is difficult to achieve on a substrate having a lower square topography, such as alignment keys used to align the patterning process. Figure 1 shows a feature 111 and a non-common formed thereon. A schematic cross-sectional view of the substrate 1 of the amorphous carbon layer 112. Since the non-conformal amorphous carbon layer U2 does not completely cover the sidewall 114 of the feature 111, subsequent etching processes may cause harmful sidewalls! The lack of complete coverage of the sidewall i 14 by the non-conformal amorphous carbon layer 112 may also cause photo-resistance poisoning of the material under the non-conformal carbon layer 112, which is known to damage electronic components. φ Therefore, there is a product available for The invention provides a method for depositing a material layer on a substrate having a topographical feature. The invention provides a method for processing a substrate. For example, by depositing an amorphous carbon layer on the substrate, the method according to a first embodiment includes disposing a substrate in a substrate processing chamber, and the ratio of carbon to hydrogenogen 6 201026877 is greater than 1: a hydrocarbon source of 2 is passed into the processing chamber, and a plasma starting gas selected from the group consisting of hydrogen, helium, argon, nitrogen, and combinations thereof is introduced into the processing chamber, and the carbon The volumetric flow rate of the hydrogen source source to the plasma starting gas has a volumetric flow ratio of 1:2 or greater 'in the treatment chamber at a rF power of 1 watt/cm 2 or less, 2 Torr or higher. And about 3 〇〇〇c to about 48 〇. The temperature of (: produces a plasma) and a conformal amorphous carbon layer is formed on the substrate. In another embodiment, a method of processing a substrate comprising performing a deposition cycle of forming a conformal amorphous carbon material on a surface of the substrate and flowing a purge gas through the processing chamber is provided 'And repeat the cycle between 2 and 50 times. In another embodiment, a method of treating a substrate comprising providing a substrate in a substrate processing chamber and passing a source of hydrocarbons having a carbon to hydrogen atom ratio of greater than 1.2 into the processing chamber is provided Electrochemical polymerization starting gas selected from one of a group consisting of hydrogen Φ gas, helium gas, argon gas, nitrogen gas, and a combination thereof is introduced into the processing chamber, and the hydrocarbon flow rate of the hydrocarbon source is The volumetric flow rate ratio of the starting gas is 1:2 or greater' wherein the hydrocarbon source and the plasma starting gas system utilize a gas distributor disposed between 400 mils and 600 mils from the surface of the substrate Passing into the processing chamber, generating a plasma in the processing chamber at an RF power of 1 watt/cm 2 or less and a temperature between about 〇 ec to about 1 〇〇 ° c and forming a total on the substrate Shaped amorphous carbon layer. 7 201026877 [Embodiment] The embodiments described herein generally provide a method of depositing an amorphous carbon material (a_c.H) having improved conformality in a chemical vapor deposition system. The conformality of a layer is typically quantified by the ratio of the average thickness of one layer deposited on the sidewalls of a feature to the average thickness of the same layer on the substrate, or the average thickness on the top surface (which can be expressed as a percentage). . It is observed that the layer deposited by the methods described herein has greater than about 3%, such as φ, such as 70°/〇 or more, about 7:1〇 or greater, such as about 80. /. Or higher, about 4: 5 or more 'to about 100%' about! : ! The conformality. For example, it will be recognized that the prior art non-conformal amorphous carbon layer 112 shown in Figure 1 has 〇% conformality because of the lack of layer deposition on the sidewall raft 14. Specifically, an improved method of conformal deposition of the a_c:H layer is provided. Conformal deposition may be achieved by using a precursor having a carbon to hydrogen ratio of 1:2 or higher, such as a carbon to hydrogen ratio of 2:3 or higher, selected from helium, hydrogen, nitrogen, argon, or The plasma of the group consisting of the composition starts with the gas with increasing precursor to plasma initial gas flow rate, with increased deposition pressure, with increased deposition temperature, with lower rf power applied, with reduced The plasma environment of the deposition rate is improved by depositing amorphous carbon in multiple layers, and combinations thereof. The deposition process can be performed in a suitable processing system. Figure 3 is a schematic illustration of a substrate processing system' system 3, which can be used to perform amorphous carbon layer deposition in accordance with embodiments of the present invention. Examples of suitable systems include the CENTURA® system, which can be used at DxZTM 8 201026877, PRECISION 5000®, PR〇DUCERTM systems such as PRODUCER SETM processing chamber and pr〇ducer GTTM processing chamber all from Santa Clara, California Applied materials company purchased. System 300 includes a process chamber 325, a gas distribution plate 33, a control unit 310, and other hardware components such as a power source and a vacuum pump. The details of one of the embodiments of the system used in the present invention are disclosed in U.S. Patent No. 6,364,954, issued April 2, 2002.

TemperatUre Chemical Vapor Deposition Chamber，，中描 述’其在此藉由引用的方式併入本文中。 該製程腔室325通常包含基材支撐座35〇，其係用來 支撐一基材，例如一半導體基材39〇。此基材支撐座35〇 在該製程腔室325内利用連接至支桿36〇的位移機構（未 不出）在垂直方向上移動。取決於製程，可在處理前先將 該半導體基材390加熱至一預期溫度^該基材支撐座35〇 係利用一嵌入式加熱器元件37〇加熱。例如，該基材支 ❹ 撐座350可藉由從一電源供應器3〇6施加電流至該加熱 器το件3 70來阻抗加熱。該半導體基材39〇轉而由該基 材支撐座3 50加熱。一溫度感應器372，例如一熱電偶， 也嵌入在該基材支撐座350内以監控該基材支撐座35〇 的溫度。測得的溫度被用於一回饋迴路中以控制用於該 加熱器元件370的電源供應器3〇6。該基材溫度可保持 或控制在選用於特定製程應用的溫度下。 使用一真空幫浦302來排空該製程腔室325並在該製 程腔室325内維持適當的氣流和壓力。一喷頭32〇，製 201026877 程氣體藉其通入製程腔室325内，係設置在該基材支撐 座3 50上方’並且適於提供均勻分佈的製程氣體至製程 腔室325内。該喷頭32〇係連接至一氣體分配盤33〇， 其控制及供應用於該製程程序不同步驟内的各種製程氣 體。製程氣體可包含一碳氫化合物來源及一電聚起始氣 體’並且在下方結合一例示氬氣稀釋沈積製程之敘述更 詳細描述。 該氣體分配盤330也可用來控制及供應各種氣化的液 態刖驅物。雖未示出’可氣化來自一液態前驅物供應源 的液態前驅物，例如，利用一液體注射蒸發器，並在載 氣存在下傳送至製程腔室325。該載氣通常是一種惰性 氣趙’例如氮氣，或一種鈍體，例如氩氣或氦氣。或者， 該液態前驅物可利用一熱及/或真空輔助氣相製程從一 安瓿氣化。 該喷頭320和基材支撐座350也可形成一對隔開的電 極。在該等電極之間產生電場時，通入腔室325内的該 等製程氣體被點燃成為電漿392。通常，該電場係利用 一匹配網路（未示出）連接該基材支揮座350至一單頻或 雙頻的射頻（RF)功率源（未示出）來產生。或者，該RF功 率源和匹配網路可連接至該喷頭320，或連接至該喷頭 320和該基材支撐座350兩者。電漿輔助化學氣相沈積 技術藉由施加電場至靠近該基材表面的反應區域，產生 一反應物種電漿來促進反應氣體的激發及/或分解。該 電漿内的物種之反應性減少發生一化學反應所需要的能 201026877 量’實際上降低此種電漿輔助化學氣相沈積製程所需的 溫度》 流經該氣體分配盤330的氣體和液體之適當控制及調 節係利用質流控制器（未示出）及例如電腦的控制單元 310來執行。該喷頭320容許來自該氣體分配盤330的 製程氣體均勻地分配及通入該製程腔室325内。例示 地’該控制單元310包含一中央處理單元（CPU)3 12、支 撐電路3 14、以及含有相關控制軟體3 16的記憶體。此 控制單元310負責基材處理所需之眾多步驟的自動控 制，例如基材傳輸、氣體流量控制、液體流量控制、溫 度控制、腔室排空等等。當該製程氣體混合物離開該喷 頭320時，該碳氫化合物的電漿辅助熱分解在該半導體 基材390表面3 95發生，致使一無定形碳層沈積在該半 導體基材390上。 沈積製程 . 本發明態樣提供a-C:H層改善的共形沈積。改善的共 形沈積可藉由使用碳對氫比例為1:2或更高的前驅物之 製程來實現’例如碳對氫比例為2: 3或更高，可利用選 自由氦氣、氫氣、氮氣、氬氣、或其組合物所組成的族 群之電漿起始氣體來實現，可以增加的前驅物對電漿起 始氣體流速來實現’可以增加的沈積壓力實現，可以增 加的沈積溫度實現，可以較低的RF功率應用實現，可利 用具有降低的沈積速率之電漿環境實現，可利用增加氣 體分配盤和基材表面之間的間距來實現，可藉由在多個 201026877 層内沈積無定形碳來實現，及其組合。咸信在此所述製 程提供降低的沈積速率及/或更等向的沈積製程，因 此，提供更為共形的沈積製程。 在沈積製程之一態樣中，一 a_C:H層係利用一製程來 形成，其包含通入一碳氫化合物來源及一電漿起始氣體 至一處理室内’例如在上面結合第3圖所述之製程腔室TemperatUre Chemical Vapor Deposition Chamber,, which is incorporated herein by reference. The process chamber 325 typically includes a substrate support 35 that is used to support a substrate, such as a semiconductor substrate 39. The substrate support 35 is moved in the process chamber 325 by a displacement mechanism (not shown) connected to the struts 36A in the vertical direction. Depending on the process, the semiconductor substrate 390 can be heated to a desired temperature prior to processing. The substrate support 35 is heated by an embedded heater element 37. For example, the substrate support holder 350 can be resistively heated by applying a current from a power supply 3〇6 to the heater τ. The semiconductor substrate 39 is twisted and heated by the substrate support holder 405. A temperature sensor 372, such as a thermocouple, is also embedded in the substrate support 350 to monitor the temperature of the substrate support 35. The measured temperature is used in a feedback loop to control the power supply 3〇6 for the heater element 370. The substrate temperature can be maintained or controlled at the temperature selected for the particular process application. A vacuum pump 302 is used to evacuate the process chamber 325 and maintain proper flow and pressure within the process chamber 325. A nozzle 32 〇 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The nozzle 32 is coupled to a gas distribution tray 33 that controls and supplies various process gases for use in different steps of the process. The process gas may comprise a source of hydrocarbon and an electropolymerization starting gas' and is described in more detail below in connection with an illustration of an argon dilution deposition process. The gas distribution plate 330 can also be used to control and supply a variety of vaporized liquid floodings. Although not shown, the liquid precursor from a liquid precursor supply can be vaporized, for example, using a liquid injection evaporator and delivered to the process chamber 325 in the presence of a carrier gas. The carrier gas is typically an inert gas such as nitrogen or a bluff body such as argon or helium. Alternatively, the liquid precursor can be vaporized from an ampoule using a heat and/or vacuum assisted vapor phase process. The showerhead 320 and substrate support 350 can also form a pair of spaced apart electrodes. When an electric field is generated between the electrodes, the process gases introduced into the chamber 325 are ignited into a plasma 392. Typically, the electric field is generated by a matching network (not shown) connecting the substrate support 350 to a single or dual frequency radio frequency (RF) power source (not shown). Alternatively, the RF power source and matching network can be coupled to the showerhead 320 or to both the showerhead 320 and the substrate support mount 350. Plasma-assisted chemical vapor deposition techniques generate a reactive species plasma to promote excitation and/or decomposition of the reactive gas by applying an electric field to a reaction zone near the surface of the substrate. The reactivity of the species in the plasma is reduced. The amount of energy required for a chemical reaction is 201026877 'actually reducing the temperature required for such a plasma-assisted chemical vapor deposition process.' Gases and liquids flowing through the gas distribution plate 330. Appropriate control and regulation is performed using a mass flow controller (not shown) and a control unit 310 such as a computer. The showerhead 320 allows process gases from the gas distribution pan 330 to be evenly distributed and passed into the process chamber 325. Illustratively, the control unit 310 includes a central processing unit (CPU) 3 12, a support circuit 314, and a memory containing associated control software 316. This control unit 310 is responsible for the automatic control of the numerous steps required for substrate processing, such as substrate transfer, gas flow control, liquid flow control, temperature control, chamber evacuation, and the like. When the process gas mixture exits the nozzle 320, plasma-assisted thermal decomposition of the hydrocarbon occurs on the surface 3 95 of the semiconductor substrate 390, causing an amorphous carbon layer to deposit on the semiconductor substrate 390. Deposition Process. Aspects of the invention provide improved conformal deposition of the a-C:H layer. Improved conformal deposition can be achieved by using a process in which a carbon to hydrogen precursor ratio of 1:2 or higher is used to achieve, for example, a carbon to hydrogen ratio of 2:3 or higher, selected from helium, hydrogen, A plasma starting gas of a group consisting of nitrogen, argon, or a combination thereof can be achieved by increasing the precursor to the plasma starting gas flow rate to achieve an increase in deposition pressure, which can be achieved by increasing the deposition temperature. , can be implemented in lower RF power applications, can be achieved with a plasma environment with reduced deposition rate, can be achieved by increasing the spacing between the gas distribution plate and the substrate surface, can be deposited in multiple layers of 201026877 Amorphous carbon is achieved, and combinations thereof. The process described herein provides a reduced deposition rate and/or an isotropic deposition process, thereby providing a more conformal deposition process. In one aspect of the deposition process, an a_C:H layer is formed using a process that includes passing a hydrocarbon source and a plasma starting gas into a processing chamber, for example, as described above in connection with FIG. Process chamber

3 25。該碳氫化合物來源係一或多種碳氫化合物，並且選 擇性地例如氬氣之載氣，的混合物。 該一或多種碳氫化合物可包含碳原子對氫原子比為 1 . 2或更尚的化合物，例如大於n 2。例如，觀察到2 : 3或更高的碳對氫（或氫的取代基，例如氟）比例，像從 3至2 : 1，例如從約2 : 3至約3 : 2，產生具有改善的 共形性之無定形碳膜層。咸信具有所述的碳對氫原子比 之此類碳氫化合物造成更為等向的沈積製程。 該等碳氫化合物可以部分或完全換雜，碳氮化合物的 衍生物也可受惠於本發明方法。衍生物包含n 氧-、氫氧根以及碳氳化合物的含硼衍生物。 般而β，可包含在該碳氫化合物來源内的碳氫化 物或其衍生物可由式CaHbFc表示，其中Α的範圍在' 和24之間’B的範圍在〇和5〇之間，c的範圍在。和 5〇之間…對B + c的比例是1:2或更高，例如大於 1:2。例如，A對B+c的比例可以是2:3或更高，例 如從2:3至2:卜並且在—進—步範例中，從2:3至 3:2。在一實施例中’其中C=〇,該碳氫化合物來源可 12 2010268773 25. The hydrocarbon source is a mixture of one or more hydrocarbons, and optionally a carrier gas such as argon. The one or more hydrocarbons may comprise a compound having a carbon atom to hydrogen atom ratio of 1.2 or more, such as greater than n 2 . For example, a ratio of carbon to hydrogen (or a substituent of hydrogen such as fluorine) of 2:3 or higher, such as from 3 to 2: 1, for example from about 2:3 to about 3:2, is observed to have improved A conformal amorphous carbon film layer. It is believed that the carbon to hydrogen atom ratio causes a more isotropic deposition process for such hydrocarbons. These hydrocarbons may be partially or completely substituted, and derivatives of carbonitrides may also benefit from the process of the invention. The derivative contains n oxygen-, hydroxide, and boron-containing derivatives of carbonium compounds. And β, a hydrocarbon or a derivative thereof which may be contained in the hydrocarbon source may be represented by the formula CaHbFc, wherein the range of Α between ' and 24' is in the range between 〇 and 5〇, c The range is. Between 5 and 5... The ratio to B + c is 1:2 or higher, for example greater than 1:2. For example, the ratio of A to B+c can be 2:3 or higher, for example from 2:3 to 2: and in the -step example, from 2:3 to 3:2. In an embodiment where 'C=〇, the hydrocarbon source can be 12 201026877

❷ 具備式CXHY，並且2/3<=x/y=<3/2 ’其中x/y是個別的 原子數。或者，就氧及/或氮取代化合物而言，該碳氫 化合物來源可用式CaHb〇cFdNe表示，其中A的範圍在 1和24之間，B的範圍在〇和50之間，c的範圍在0和 10之間’ D的範圍在〇和50之間，E的範圍在〇和1〇 之間’而A對B+C+D+E的比例是1 : 2或更高，例如大 於1 : 2。例如，A對B + C+D+E的比例可以是2 : 3或更 高，例如從2:3至2: 1，並且在一進一步範例中，從2: 3 至 3 : 2。 適合的碳氫化合物包含一或多種如下化合物，例如， 炔，像乙炔（C2H2)，乙烯乙炔及其衍生物，芳香族碟氫 化合物，例如苯、苯乙烯、甲苯、二甲苯、吡啶、乙苯、 苯乙鲷、苯甲酸甲酯、乙酸苯酯、酚、甲酚、吱喃、以 及諸如此類，α -松油烯，異丙基甲苯，1，1，3,3，_四甲基 丁苯，第三丁醚，甲基丙烯酸甲酯，以及第三丁基糖基 醚，具備式CsH2和C5H4的化合物，鹵化的芳香族化合 物，包含氟苯、二氟苯、四氟苯、六氟苯及諸如此類。 其它適合的碳氫化合物包含烯，例如乙烯、丙歸、丁婦、 戊婦、及諸如此類’二稀，例如丁二烯、異戊二稀、戊 二婦、己二稀及諸如此類，以及由化的缔，包含氣乙稀、 二氟乙烯、三氟乙烯、四氟乙烯、氣乙烯、二氯乙稀、 三氟乙烯、四氯乙烯、以及諸如此類。碳原子對氣原子 比大於1: 2的前驅物之一範例是CUH2 ’其可以是丁 _ 炔。 13 201026877 此外，本發明預期使用碳原子對氫原子比為3:〖或更 高的前雜物’像5: 1，例如1〇: 1或更高。 咸信隨著礙對氫比例增加，碳原子會在沈積期間與相 鄰的碳原子鍵結，藉由形成複雜的三維短程結構網路而 造成沈積膜較佳的共形性。 該a-C:H沈積製程包含使用一種電漿起始氣體，其係 在該碳氫化合物之前及/或與其同時通入該腔室，並且 起始一電漿以開始沈積。該電漿起始氣體可以是一種高 游離電位氣趙’包含但不限於’氦氣、氫氣、氮氣、氬 氣及其組合物’其中氦氣是較佳的。該電漿起始氣體也 可以是一種化學惰性氣體，例如氦氣、氮氣、或氬氣是 較佳的。適合的氣體游離電位是從約5 eV(電子電位）至 25 eV。該電漿起始氣體可在該碳氫化合物之前通入該腔 室内，這容許形成穩定的電漿並降低電弧的可能性。已 觀察到使用具有高游離電位的電漿起始氣體可在沈積期 間提供較少的薄膜非等向性蝕刻，因此改善無定形碳膜 沈積的共形性。做為稀釋氣體或載氣的惰性氣體，例如 氬氣，可連同該電漿起始氣體、該碳氫化合物、或其組 合物一起通入^ 該碳氫化合物和電漿起始氣體可以從約1:100或更高 的碳氫化合物對電漿起始氣流比例通入，例如，從約i : 100至100 : 1，像就該無定形碳沈積而言從約1 : 10至 約10:1。在一實施例中，該碳氫化合物對電漿起始氣 流比例可從約1 : 5或更高，像從約1 : 5至約2 : 1，例 201026877 如從約I:2至約I:1，可用於該無定形碳沈積。已觀 察到增加碳氫化合物對電漿電漿起始氣流比例可提供優 於較低比例的改善之共形性。 該a-C:H層可從該處理氣鱧沈積，藉由將腔室壓力保 持在約2托耳或更高，例如從約2托耳至約2〇托耳，並 且在一實施例中，約7托耳或更高，例如從約7托耳至 約9托耳。已觀察到共形性隨著壓力增加而增加，並且 攀 咸信離子在抵達該基材之前更為分散，因此喪失一些姓 刻能力’並且更為分散的自由基以更隨機且等向的角度 抵達該基材表面，以利更加等向且共形的薄膜沈積。 該a-C:H層可在基材溫度維持在從約〇。〇至約8〇〇。(：的 腔室内從該礙氫化合物來源沈積，例如在從約〇。〇至約 100°C的溫度下’或在從約30(TC至約480°C的溫度下， 例如，從約400°C至約450。(：。已觀察到在增加的溫度下 沈積無定形碳膜層會降低沈積速率，因此改善共形性。 ❹ 此外，在增加的溫度下’吸附的碳前驅物之擴散性或流 動性會增加，導致更加等向的沈積和改善的共形性。 此外，該a-C:H層也可以更為共形的方式沈積，當該 層係在將基材溫度維持在低於約1 〇〇°C的腔室内從該碳 氫化合物來源沈積時。例如，一 a-C:H層係藉由透過與 該基材表面隔開310密爾的噴頭提供3800 seem的C2H2 及6000 seem的氦氣至維持在9托耳壓力以及75 °C下的 製程腔室，並藉由應用30瓦的高頻功率產生電漿來沈 積。分析的沈積層展現出77.8%的共形性（共形性的量度 15 201026877 係定義為沈積在一特徵結構的側壁上之無定形碳層的平 均厚度s對基材上表面上的無定形碳層的平均厚度τ的 比例）。同樣地，也觀察到該特徵結構底部上的無定形碳 層的厚度對比於基材上表面上的無定形碳層的厚度T的 比例是72.2%。 同時驚人且不預期地發現到在降低的氦氣流逮下，例 如約3000 sccm的氦氣’溫度低於1〇〇。〇的沈積在—特徵 結構定義底部上的沈積厚度方面產生實質改#，與在密 集的特徵結構定義，即每16〇〇平方奈米約9個特徵結構 上之該特徵結構底部上的無定形碳層之厚度對比於基材 上表面上的無^形碳層的厚度τ之比例是72以相比。 也觀察到所沈積的無定形碳層之共形性隨著沈積該層 時該喷頭和基材表面間的間距增加而改善，例如介於· 密爾和600密爾之間的間距，例如約5〇〇密爾的間距。 例如，-第二無定形碳層與前段在相同的低溫沈積條件 下沈積，但是該喷頭間距為5〇〇密爾，與31〇密爾相較。 分析的沈積之第二層展現出9().9%至9ι 7%的共㈣（共 形性的量度係定義為沈積在—特徵結構的侧壁上之盖定 形碳層的平均厚度S對基材上表面上的無定形碳層的平 均厚度Τ的比例）。同樣地，也觀察到在具有不同密度的 特徵結構圊案上，例如密集的特徵結構定義，即每1600 平方奈米約4至2〇個特徵結構，例如9個特徵結構定 義，對比於較不密集的，每16〇〇平方奈米低於4個特徵 結構定義’例如1個特徵結構定義，的特徵結構定義， 16 201026877 該特徵結構底部上的無定形碳層的厚度對比於基材上表 面上的無定形碳層的厚度τ的比例是9〇 9%至91 7%，。 也觀察到該500密爾間距的無定形碳層具有約138埃 /分鐘的沈積速率，與該310密爾間距的沈積製程之3〇〇 埃/分鐘的沈積速率相比。 該碳氫化合物纟源及-電漿起始氣體係經通入該腔室 内，並且起始一電漿以開始沈積。可用一雙頻rf i生該電咸信一雙頻RF功率應用可提供通量和離子 能量的獨立控制，因為咸信衝擊該薄膜表面的該等離子 之能量會影響薄膜密度。相信該高頻電浆控制電衆密 度，而一低頻電漿控制衝擊該基材表面的離子之動能。 具有混合的RF功率之雙頻來源提供範圍從約1〇厘112至 約30MHz的高頻功率，例如約13 56 MHz，以及範圍從 約10 kHz至約1 MHz的低頻功率，例如約35〇 kHz。當 使用一雙頻RF系統來沈積一 a_c:H膜時，該第二RF# φ 率對總混合頻率功率的比例較佳地低於約0.6至 1.0(0.6.1)。可基於基材尺寸和所用設備來改變所施加的 RF功率和一或多種頻率的使用。可使用一單頻功率 應用’並且通常是應用如在此所述之高頻功率。 可藉由施加功率密度對基材表面積從約〇〇1瓦/平方 公分至約5瓦/平方公分的RF功率來產生電漿，例如從 約〇·01至約1瓦/平方公分，例如約0.1瓦/平方公分。 就一 300亳米的基材而言，該功率應用可從約ι瓦至約 2000瓦’例如從約瓦至約200瓦，例如約20瓦。電 17 201026877 極間距，即該基材和該喷頭之間的距離，可以是從約200 密爾至約1000密爾。 雖未遵循任何特定理論，但相信電漿製程藉由減少能 量化離子數目來降低無定形碳沈積速率，使碳氫化合 物，即自由基’以更隨機的沈積圖案抵達該基材表面， 因此提供所形成的薄膜成長更等向的沈積圖案而改善共 形性。也觀察到該降低的電漿沈積可提供較低的沈積速 率’其容許吸附的碳前驅物在該基材表面上擴散，而提 ·#更為共形的膜層。 處理300毫米圓形基材之一例示沈積製程運用一種電 聚起始氣體’例如氦氣’及一種碳氫化合物來源，例如 乙炔（CzH2)。該製程可包含供應流速從約4〇〇 sccm至約 8000 SCCm的電漿起始氣體，例如氦氣，供應流速從約 400 seem至8000 seem的碳氳化合物來源，例如乙炔 (CzH2)，施加從約1〇瓦至約2000瓦的雙頻111?功率，將 φ 腔至壓力維持在從約2托耳至約20托耳，以及將腔室溫 度維持在從約25°C至約475°C。此製程範圍提供a_C:H 層範圍在約10埃/分鐘至約30000埃/分鐘内的沈積速 率以及從約30%至約100%的共形性（沈積在一特徵結構 側壁上之一層的平均厚度對相同沈積層在該基材範圍， 或上表面，上的平均厚度之比例）。熟知技藝者，在閱讀 此間揭示後，可計算出適當的製程參數，以製造沈積速 率不同的a-C:H膜。 在該沈積製程之一實施例中，執行複數個獨立的無定 18 201026877 形碳沈積以形成一無定形碳層。在該複合沈積製程之一 態樣中’-沈積步驟，如在此所述者之後緊接一暫停 ，驟’其中電漿起始氣體、—稀釋氣體、及/或前驅物 可乂降低或無沈積速率的狀態流通。適合的電裝起始氣 鱧、稀釋氣體、及/或前驅物可以從約1〇〇 s_至約 40000 seem的流速通入該腔室内。若使用該電漿起始氣 體即/或-稀釋氣體，可為該暫停步驟起始__電聚。該 ❹沈積和暫停步驟然、後可重複直到得到預期厚度為止，並 且可以循環1至100次，例如循環1〇至5〇次例如循 環30次，或者是沈積約1%至約1〇〇%之間的無定形碳材 料厚度，例如從約2。/。至約10%的循環，例如約3 3%。 一獨立週期的每一次循環可沈積從約1埃至約1〇〇〇埃厚 的無定形碳材料’以形成厚度從約1〇埃至約15〇〇〇埃的 無定形碳層。該循環沈積製程可使用一或多種上述製程 參數調整。 φ 或者，也可抽出氣體，然後在沈積步驟之前或暫停步 驟期間再次通入。 咸信一多層沈積方案會降低有效薄膜沈積速率，改善 共形性。此外，新沈積的碳原子可在該暫停步驟期間擴 散，更進一步改善共形性❶一般而言，共形性在一特定 無定形碳膜層厚度的層數量增加時（較薄的個別層厚度 及較多次重複），並且在暫停步驟時間對沈積步驟時間的 比例較大時（低的有效沈積速率）獲得改善。例如，暫停 步驟時間對沈積步驟時間的比例可從約100 : 1至約！： 1 〇〇。藉由調整各別層的厚度和暫停對沈積時間比例，可 19 201026877 調整無定形碳膜層的共形性 另一種樞紐以改善一特定電 條件（前驅物、氡體、流速、 共形性。 以符合元件需求，因而提供 衆輔助化學氣相沈積之沈積 壓力、溫度、RF功率等）的 本發明方法之—± 轨+ 主要優勢在於優於其他a-C:H沈積製 程的共形性增強，如笙？阁拼- , 如第2圖所不。第2圖示出具有一特 徵結構2(Π及-無定形碳層2()2形成在其上的基材細 之概要面圖。無定形碳層202示出利用本發明方法沈 帛薄膜的’、型外觀。就質而言，無定形碳層202係高 度共形且το全覆蓋特徵結構2〇1的侧壁和底部Μ〗。 就量而言，無定形碳層2〇2可擁有從約3〇%至約1〇〇%等 級的共形性。例如從約鳩至約9G%，其中共形性（共形 性董度）係定義為沈積在側壁2〇4上的無定形碳層2〇2之 平均厚度S對基材200上表面205上的無定形碳層2〇2 之平均厚度T的比例。再參見第！圖，非共形之無定形 碳層202係經示為具有約5%的共形性。 利用在此所述製程沈積之無定形碳材料的範例如下。 ® 比較範例A: 一供比較的無定形碳沈積製程範例包含 提供約400 seem的氦氣流速至該處理室，約8〇〇() sccm 的氬氣流速至該處理室’提供約6000 seem的C3H6流速 至該處理室，施加約1250瓦的高頻rf功率（13 56 MHz) ’將沈積溫度維持在約3〇〇它，將腔室壓力維持在 約4.5托耳’連同約380密爾的間距以在密集區域上以 及開放區域階梯覆蓋（共形性量度）產生共形性約2〇%的 無定形碳層。 在一第一範例中，藉由提供約4000 sccrn的氦氣流速 20 201026877 ^該處理室，提供約2000 sccm的C#2流速至該處理 至’施加約50瓦的高頻RF功率（13.56 MHz)，將沈積溫 度維持在約400。(：，將腔室壓力維持在約9托耳，連同 約3〇〇密爾的間距來沈積一無定形碳層，產生187埃/ 分鐘的沈積速率，並且觀察到達成密集區域約83%至開 放區域階梯覆蓋（共形性量度）約96%的共形性。所有範 例皆在深寬比約2.1:1的特徵結構上執行。 在第一範例中，藉由提供約2000 seem的氦氣流速 至該處理室，提供約200〇 seem的C2H2流速至該處理 ® 室，施加約100瓦的高頻RF功率（13.56 MHZ)，將沈積 溫度維持在約400°C，將腔室壓力維持在約9牦耳，連 同約300密爾的間距來沈積一無定形碳層，產生516埃 /分鐘的沈積速率，並且觀察到達成密集區域約82%至 開放區域階梯覆蓋（共形性量度）約86%的共形性。該第 一範例及該第二範例皆在深寬比約2.1:1的特徵結構上 執行。 在一第三範例中，藉由提供約4000 sccm的氦氣流速 © 至該處理室，提供約2000 sccm的C2HZ流速至該處理 室，施加約20瓦的高頻RF功率（13 56 MHz)，將沈積溫 度維持在約400。(：，將腔室壓力維持在約9托耳，連同 約300密爾的間距來沈積一無定形碳層，產生64埃/分 鐘的沈積速率，並且觀察到達成密集區域約93%至開放 區域階梯覆蓋（共形性量度）約97%的共形性。 在一第四範例中，藉由提供約4000 sccm的氦氣流速 至該處理室，提供約2000 seem的CzH2流速至該處理 室，施加約1〇〇〇瓦的高頻RF功率（13 56 MHz)，將沈積 21 201026877 溫度維持在約40(rc，將腔室壓力維持在約7托耳，連 同約31〇密爾的間距來沈積一無定形碳層。 在一第五範例中’利用沈積步驟之後緊接氦氣淨化步 驟之丨4次沈積循環來沈積一無定形碳層，該沈積步驟提 供約4〇〇〇 scem的氦氣流速至該處理室提供約2〇⑽ m的C2H2流速至該處理室’施加約1 〇〇瓦的高頻rf 功率（13.56 MHz)，將沈積溫度維持在約3〇〇t：，將腔室 壓力維持在約9托耳，連同約300密爾的間距，產生9〇9 埃/分鐘的沈積速率，並且觀察到達成約84%的密集區 域覆蓋（共形性量度）。該氦氣淨化步驟係在相同製程參 數下執行，除了無流並且無施加RF功率之外。 在一第六範例中，利用沈積步驟之後緊接氦氣淨化步 驟之14 _人沈積循環來沈積一無定形碳層。該沈積步驟提 供約400 seem的低氦氣流速至該處理室，提供約4〇〇 seem的C2H2流速至該處理室，施加約1〇〇瓦的高頻好 功率（13.56 MHz)’將沈積溫度維持在約3G(rc，將腔室 壓力維持在約7托耳，連同約3〇〇密爾的間距，產生9〇9 粵埃/刀鐘的沈積速率，並且觀察到達成約。的側壁對 頂。P共形性’ 94%的側壁對底部共形性以及72%的底部 f頂°卩共形性。該氦氣淨化步驟係在相同製程參數下執 行除了無C2H2流並且無施加rf功率之外。 ，在第七範你J中，進行在不同功率範圍下沈積的無定 形碳層之比較。就兩個製程而言藉由提供約糊〇 的氦氣流速至該處理室，提供約2〇〇〇 的c而流速 〇該處理室’施加約5〇瓦或2〇瓦的高頻功率⑴％ Hz)將沈積溫度維持在約4〇〇。〇，將腔室壓力維持在 22 201026877 =9托耳’連同約3⑻密爾的間距來沈積該無定形礙。 =0瓦沈積製程以沈積速率細埃/分鐘產生㈣的側 對頂部共形性，而該2G瓦沈積製程以沈積速率64埃 /刀鐘產生93-970/〇的側壁對頂部共形性。 在一第八範例中，進行循環相對於單一步驟沈積所沈 積出的無定形碳層之比較。就兩個製程而言藉由提供 約4000 sccm的氦氣流速至該處理室提供約“ο。 的QH2流速至該處理室，施加約1〇〇瓦的高頻rf功率 (56 MHz)，將沈積溫度維持在約4〇〇乞，將腔室壓力 維持在約9托耳’連同約3〇〇密爾的間距來沈積該無定 形碳。該單—步驟沈積製程產生51%的側壁對頂部共形 性87/〇的側壁對底部共形性以及59%的底部對頂部共 形性。包含沈積之後緊接一氦氣淨化步驟之14次循環的 循環沈積步驟產生71%的側壁對頂部共形性，92%的側 壁對底部共形性以及77%的底部對頂部共形性。該氦氣 淨化步驟係在相同條件下執行，除了無施加RF功率並且 不提供C2H2之外。 • 在一第九範例中，進行兩種循環製程相對於單一步驟 沈積所沈積出的無定形碳層之比較。就兩個製程而言， 藉由提供約4000 sccm的氦氣流速至該處理室提供約 2000 seem的qH2流速至該處理室，施加約5〇瓦的高頻 RF功率（13.56 MHz)，將沈積溫度維持在約4〇〇〇c，將腔 室壓力維持在約9托耳，連同約300密爾的間距來沈積 該無定形碳。該單一步驟沈積製程使用25瓦的RF功率 應用並產生密集結構之56%的侧壁對頂部共形性及開放 結構之87%的側壁對頂部共形性。該第一循環製程之第 23 201026877 一循環處理系列使用25次持續7秒、每一者20埃之上 述沈積和氦氣冷卻循環’產生密集結構之5 5 %的側壁對 頂部共形性及開放結構之82%的側壁對頂部共形性；而 該第二系列使用10次持續15秒、每一者50埃之沈積和 氦氣循環，產生密集結構之54%的側壁對頂部共形性及 開放結構之7 5 %的侧壁對頂部共形性。該第二製程之第 一循環處理系列使用25次每一者20埃之七秒鐘的沈積 循環，產生密集結構之78%的側壁對頂部共形性及開放 結構之89%的側壁對頂部共形性；該第二系列使用1〇次 每一者50埃之十五秒鐘的沈積循環，產生密集結構之 69%的側壁對頂部共形性及開放結構之89%的側壁對頂 邛共形性，而該第三系列使用25次每一者20埃之七秒 鐘的沈積和13秒鐘的穩定步驟循環，產生密集結構之 55%的侧壁對頂部共形性及開放結構之92%的側壁對頂 部共形性。 第4A-41圖係使用在此所述之無定形碳層蝕刻一材料 層之製程的概要側視圖。在一基材表面（未示出）上沈積 _ 。基底材料41〇,以開始形成一材料堆疊40(^該基底材 料可以是用來形成半導體元件之一或多種材料，包含矽 基材材料、氧化物材料、多晶石夕材料或諸如此類。在 該基底材料410上沈積一第一無定形碳層42〇,並且在 該第一無定形碳層420上沈積一第一抗反射層材料 430,如第4B圓所示。該無定形碳層可以是能夠從加州 聖塔克拉扳的應用材料公司購得之先進曝光圖樣薄膜 (APF)材料’或者’如在此所述之無定形碳材料。該第一 抗反射層材料43G係用來在微影圖案化製程期間控制光 24 201026877 線反射。該第一抗反射層材料43 0可包含二氧化矽、氧 氮化矽、氮化矽、或其組合物。該抗反射層材料可以是 勺從加州聖塔克拉拉的應用材料公司購得之darcTM 材料層。 可在該第一抗反射層材料上依序沈積一第二無定形碳 層440和一第二抗反射層材料45〇，如第圖所示。該 第一無疋形碳層440和該第二抗反射層材料 450可以是 如沈積層420和帛一抗反射層材#43〇者相同的材料。 然後在該第二抗反射層材料450上沈積一光阻層46〇， 例如光阻劑材料，如第4D圖所示。然後利用一微影製 程圖案化該光阻層’產生一圖案化光阻層461，如第4e 圖所不。形成在該光阻層461内的第一圖案462係利用 一或多個蝕刻製程首先蝕刻該第二抗反射層材料45〇， 然後蝕刻該第二無定形碳層44〇來轉移至該第二無定形 碳層440，而形成一圖案化的第二無定形碳層441〇如第 4F圖所不。該圖案化的第二無定形碳層441可做為下方 材料的硬光罩。該第二抗反射層材料45〇可利用該一或 # 多個餘刻製程或利用一分開的製程移除》 在該第一抗反射層材料430和該圖案化的第二無定形 碳層441上沈積一共形的無定形碳層47〇，如第4G圖所 示。該共形的無定形碳層可利用在此所述之任何製程沈 積。利用一非等向蝕刻製程圖案化該共形的無定形碳層 470 ’以提供側壁無定形碳材料471，如第々η圖所示。 該侧壁無定形碳材料471的存在容許第二圖案472形 成，其具有與否則可在正常情況下利用現行微影製程實 現者相比縮小的關鍵尺寸和特徵結構尺寸，即增加的圖 25 201026877 案密度。該圖案化的第二無定形碳層441結合該側壁無 定形碳材料471可做為下方的第一抗反射層材料43〇和 該第一無定形碳層420的硬光罩層。 然後钱刻該第一抗反射層材料43〇以形成具有該第二 圖案472之圖案化抗反射層431，如第41圖所示。在該 蝕刻製程期間或利用一後續製程除去該圖案化的第二無 定形碳層441和該側壁無定形碳材料471。然後蝕刻該 第一無定形碳層420以形成具有欲轉移至下方基底材料 410的第二圖案472之圖案化的第一無定形碳層421。然 • 後利用該圖案化的第一無定形碳層421做為硬光罩層來 蝕刻該基底材料410，如第4K圖所示，接著除去該圖案 化的第一無定形碳層421以提供含有具備該第二圖案 472的圖案化基底材料4Π之基材表面，如第圖所示。 在另一實施例中，為第4F-4L圖使用一圖案化光阻材 料來取代該圖案化的第二無定形碳層441，因此除去對 於第4C-4E圖之該圖案化的第二無定形碳層44〇和一第 一抗反射層材料450以及對應的沈積步驟和蝕刻步驟的 ❹ 需要。 第5A-5H圖係在一空間光罩雙重圖案化製程内使用在 此所述之無定形碳層之製程的概要側視圖。在一基材表 面上沈積一基底材料510,以開始形成一材料堆疊5〇〇。 該基底材料可以是用來形成半導體元件之一或多種材 料，包含矽基材材料、氧化物材料、多晶矽材料、或諸 如此類。在該基底材料510上沈積一第一無定形碳層 520’並且在該第一無定形碳層52〇上形成具有一第一圓 案532的圖案化光阻層530,如第5A圖所示》該無定形 26 201026877 碳層可以是能夠從加州聖塔克拉拉的應用材料公司靖得 之先進曝光圖樣薄膜（APF)材料，或者，如在此所述之無 定形碳材料。可利用一微影製程來圖案化該光阻層53〇1 然後使該圖案化光阻層530經受一修整製程藉此窄化 該圖案化光阻材料的寬度而形成由該經修整的光阻材料 31界疋之第一圖案533，如第5B圖所示。然後钱刻該 第一無定形碳層520以轉移該第二圖案533，而形成一 圖案化的無定形碳層521，如第5c圖所示。 % 然後鄰接該圖案化的無定形碳層521結構形成側壁間 隙壁540。間隙壁可包含一種蝕刻速率與該第一無定形 碳層或共形的無定形碳材料不同的可蝕刻材料。適合的 材料包含，例如，二氧化矽、氧氮化矽、氮化矽、或其 組合物《然後在該等侧壁間隙壁54〇及圖案化的無定形 碳層521結構上沈積共形的無定形碳材料之縫隙填補層 550，如第5E圖所示。可利用在此所述之任何製程來沈 積該共形的無定形碳材料。較佳的共形的無定形碳材料 是蝕刻性質與圖案化的無定形碳層521相似者。然後回 蝕該縫隙填補層550以暴露出該等側壁間隙壁540，如 第5F圖所示。接著蝕刻該等側壁間隙壁54〇以暴露出基 底材料510,界定出一硬光罩層551，如第5G圖所示。 然後可圖案化蝕刻該基底材料51〇以形成一圖案化基底 材料511 ’如第5H圖所示。 在另一製程中，在如第5D圖所示般鄰接該圖案化的無 定形碳層521結構形成該等側壁間隙壁54〇之後，接著 將該圖案化的無定形碳層521從該基材表面去除。該等 側壁間隙壁540於是形成一圖案，如第5E，所示，其可 27 201026877 用來做為該基底材料510的硬光罩。接著可圖案化蝕刻 該基底材料51〇以形成一圖案化基底材料511。 第6A-6J圖係使用在此所述之無定形碳層來蝕刻一材 料層，例如利用低於100度的無定形碳沈積製程，的製 程之概要侧視圖。在一基材表面（未示出）上沈積一基底 t料610,以開始形成一材料堆疊6〇(^該基底材料可以 疋用來形成半導體元件之一或多種材料包.含矽基材材 料、氧化物材料、多晶矽材料、或諸如此類。在該基底 材料610上沈積一第一無定形碳層620，並且在該第一 無定形碳層620上沈積一抗反射層材料63〇,如第66圖 所示。該無定形碳層可以是能夠從加州聖塔克拉拉的應 用材料公司購得之先進曝光圖樣薄膜（APF)材料，或者， 如在此所述之無定形碳材料。該抗反射層材料63〇係用 來在微影圖案化製程期間控制光線反射。該抗反射層材 料630可包含二氧化矽、氧氮化矽、氮化矽、或其組合 物。該抗反射層材料可以是能夠從加州聖塔克拉拉的應 用材料公司購得之DARC™材料層。 ® 然後在該抗反射層材料630上沈積一光阻層640，例 如一光阻劑材料’如第6C圖所示。接著利用一微影製程 圖案化該光阻層’產生一圖案化光阻層641，如第6〇圖 所示。該圖案化光阻層641形成一第一蝕刻圖案642。 利用在此所述製程及共形性共形地或實質上共形地在 該圖案化光阻層641上沈積一第二無定形碳層65〇,如 第6E圖所示。該共形的無定形碳層可利用在此所述之任 何製程沈積。在一範例中，該第二無定形碳材料係利用 低於100°C的沈積製程沈積。餘刻並圖案化該第二| 乃' """ 28 201026877 形碳層650以形成一第二蝕刻圖案652，其具有比該第 一蝕刻圖案縮小的，例如較窄的，特徵結構尺寸如^第 6F圖所不。利用一非等向蝕刻製程圖案化該共形的第二 無定形碳層650，以提供側壁無定形碳材料651。具备 has the formula CXHY, and 2/3<=x/y=<3/2 ’ where x/y is the number of individual atoms. Alternatively, in the case of oxygen and/or nitrogen substituted compounds, the hydrocarbon source may be represented by the formula CaHb〇cFdNe, wherein A ranges between 1 and 24, B ranges between 〇 and 50, and c ranges from The range of 'D between 0 and 10 is between 〇 and 50, the range of E is between 〇 and 1〇' and the ratio of A to B+C+D+E is 1: 2 or higher, for example greater than 1 : 2. For example, the ratio of A to B + C + D + E can be 2: 3 or higher, for example from 2:3 to 2: 1, and in a further example, from 2:3 to 3:2. Suitable hydrocarbons include one or more of the following compounds, for example, alkynes such as acetylene (C2H2), ethylene acetylene and its derivatives, aromatic dish hydrogen compounds such as benzene, styrene, toluene, xylene, pyridine, ethylbenzene , phenethyl hydrazine, methyl benzoate, phenyl acetate, phenol, cresol, decyl, and the like, α-terpinene, isopropyl toluene, 1,1,3,3,4-tetramethylbutylbenzene , a third butyl ether, methyl methacrylate, and a third butyl glycosyl ether, having a compound of the formula CsH2 and C5H4, a halogenated aromatic compound, comprising fluorobenzene, difluorobenzene, tetrafluorobenzene, hexafluorobenzene And so on. Other suitable hydrocarbons include alkenes such as ethylene, propylene, dimethoate, pentane, and the like, such as butadiene, isoprene, pentamethylene, hexamethylene, and the like, and The inclusion of ethylene, difluoroethylene, trifluoroethylene, tetrafluoroethylene, ethylene, ethylene, dichloroethylene, trifluoroethylene, tetrachloroethylene, and the like. An example of a precursor having a carbon to gas ratio of greater than 1:2 is CUH2' which may be a 1,4-alkyne. Further, the present invention contemplates the use of a carbon atom to hydrogen atom ratio of 3: [or higher precursors] like 5: 1, for example, 1 〇: 1 or higher. As the ratio of hydrogen increases, carbon atoms are bonded to adjacent carbon atoms during deposition, resulting in better conformality of the deposited film by forming a complex three-dimensional short-range network. The a-C:H deposition process involves the use of a plasma starting gas that passes into the chamber before and/or at the same time as the hydrocarbon and initiates a plasma to initiate deposition. The plasma starting gas may be a high free potential gas, including but not limited to 'helium, hydrogen, nitrogen, argon, and combinations thereof' wherein helium is preferred. The plasma starting gas may also be a chemically inert gas such as helium, nitrogen, or argon. A suitable gas free potential is from about 5 eV (electron potential) to 25 eV. The plasma starting gas can pass into the chamber before the hydrocarbon, which allows for the formation of a stable plasma and reduces the likelihood of arcing. It has been observed that the use of a plasma starting gas having a high free potential provides less film anisotropic etching during deposition, thereby improving the conformality of amorphous carbon film deposition. An inert gas, such as argon, as a diluent gas or a carrier gas may be introduced together with the plasma starting gas, the hydrocarbon, or a combination thereof. The hydrocarbon and the plasma starting gas may be from about A ratio of 1:100 or higher hydrocarbon to plasma initial gas flow, for example, from about i: 100 to 100: 1, from about 1:10 to about 10 for the amorphous carbon deposition: 1. In one embodiment, the ratio of hydrocarbon to plasma initial gas flow can be from about 1:5 or higher, such as from about 1:5 to about 2:1, such as 201026877, from about I:2 to about I. : 1, can be used for the amorphous carbon deposition. It has been observed that increasing the proportion of hydrocarbons to the initial flow of plasma plasma provides better conformality than a lower ratio. The aC:H layer can be deposited from the process gas by maintaining the chamber pressure at about 2 Torr or higher, such as from about 2 Torr to about 2 Torr, and in one embodiment, about 7 Torr or higher, for example from about 7 Torr to about 9 Torr. It has been observed that conformality increases with increasing pressure, and that the salty ion is more dispersed before it reaches the substrate, thus losing some of the more capable and more dispersed free radicals at a more random and isotropic angle. Arriving on the surface of the substrate to facilitate more isotropic and conformal film deposition. The a-C:H layer can be maintained at a substrate temperature of about 〇. 〇 to about 8 〇〇. (where the chamber is deposited from the hydrogen barrier compound source, for example at a temperature from about 〇. 〇 to about 100 ° C' or at a temperature of from about 30 (TC to about 480 ° C, for example, from about 400) °C to about 450. (: It has been observed that depositing an amorphous carbon film layer at an increased temperature reduces the deposition rate and thus the conformality. ❹ In addition, the diffusion of the adsorbed carbon precursor at increased temperatures Sex or fluidity increases, resulting in more isotropic deposition and improved conformality. In addition, the aC:H layer can also be deposited in a more conformal manner when the layer is maintained at a substrate temperature below A chamber of about 1 〇〇 ° C is deposited from the hydrocarbon source. For example, an aC:H layer provides 3800 seem C2H2 and 6000 seem by passing through a nozzle spaced 310 mils from the surface of the substrate. Helium gas was maintained at a process pressure of 9 Torr and 75 ° C and was deposited by applying a high frequency power of 30 watts. The deposited layer exhibited a conformality of 77.8% (conformal) The measure of sex 15 201026877 is defined as the amorphous carbon deposited on the sidewall of a feature structure. The ratio of the average thickness s to the average thickness τ of the amorphous carbon layer on the upper surface of the substrate.) Similarly, the thickness of the amorphous carbon layer on the bottom of the feature is also observed as compared to the absence on the upper surface of the substrate. The ratio of the thickness T of the shaped carbon layer is 72.2%. At the same time, it is surprisingly and unexpectedly found that under the reduced helium flow, for example, the helium gas temperature of about 3000 sccm is lower than 1 〇〇. Defining the thickness of the deposit on the bottom produces a substantial change, compared to the thickness of the amorphous carbon layer on the bottom of the feature structure in a dense feature definition, ie about 9 features per 16 square nanometers. The ratio of the thickness τ of the carbon-free carbon layer on the upper surface of the material is 72. The conformality of the deposited amorphous carbon layer is also observed as the surface between the showerhead and the substrate is deposited as the layer is deposited. The pitch is increased and improved, for example, a pitch between mil and 600 mils, for example, a pitch of about 5 mils. For example, the second amorphous carbon layer is deposited under the same low temperature deposition conditions as the front segment. But the nozzle spacing is 5〇〇 Er, compared to 31 mil. The second layer of the deposited deposit exhibits a total of 9 ().9% to 9 ι 7%. (The measure of conformality is defined as the deposition on the sidewall of the feature structure. Covering the ratio of the average thickness S of the shaped carbon layer to the average thickness Τ of the amorphous carbon layer on the upper surface of the substrate.) Similarly, it is also observed that in characteristic structures having different densities, such as dense features Definition, ie about 4 to 2 features per 1600 square nanometers, for example 9 feature structure definitions, compared to less dense, less than 4 feature structure definitions per 16 square nanometers 'eg 1 feature Structural definition, definition of characteristic structure, 16 201026877 The ratio of the thickness of the amorphous carbon layer on the bottom of the characteristic structure to the thickness τ of the amorphous carbon layer on the upper surface of the substrate is 9〇9% to 91 7%. It was also observed that the 500 mil pitch amorphous carbon layer had a deposition rate of about 138 angstroms per minute compared to the deposition rate of 3 angstroms per minute of the 310 mil pitch deposition process. The hydrocarbon helium source and the plasma starting gas system are passed into the chamber and a plasma is initiated to initiate deposition. A dual-frequency RF power application can be used to provide independent control of flux and ion energy, since the energy of the plasma that impacts the surface of the film affects the film density. It is believed that the high frequency plasma controls the electrical density, while a low frequency plasma controls the kinetic energy of the ions that impact the surface of the substrate. A dual frequency source with mixed RF power provides high frequency power ranging from about 1 112 112 to about 30 MHz, such as about 13 56 MHz, and low frequency power ranging from about 10 kHz to about 1 MHz, such as about 35 kHz. . When a dual frequency RF system is used to deposit an a_c:H film, the ratio of the second RF# φ rate to the total mixed frequency power is preferably less than about 0.6 to 1.0 (0.6.1). The applied RF power and the use of one or more frequencies can be varied based on the size of the substrate and the equipment used. A single frequency power application can be used' and typically the application of high frequency power as described herein. The plasma can be generated by applying a power density to the RF power of the substrate surface area from about 1 watt/cm 2 to about 5 watts/cm 2 , for example from about 〇·01 to about 1 watt/cm 2 , for example, about 0.1 watt / square centimeter. For a 300 mil substrate, the power application can range from about 10,000 watts to about 2,000 watts, such as from about watts to about 200 watts, such as about 20 watts. Electrical 17 201026877 The pole spacing, i.e., the distance between the substrate and the showerhead, can be from about 200 mils to about 1000 mils. Although not following any particular theory, it is believed that the plasma process reduces the rate of amorphous carbon deposition by reducing the number of energized ions, allowing hydrocarbons, ie, free radicals, to reach the surface of the substrate in a more random deposition pattern, thus providing The formed film grows in a more isotropic deposition pattern to improve conformality. It has also been observed that this reduced plasma deposition provides a lower deposition rate' which allows the adsorbed carbon precursor to diffuse over the surface of the substrate while providing a more conformal film layer. One of the processes for treating a 300 mm circular substrate is that the deposition process utilizes an electropolymerization starting gas 'e.g., helium' and a hydrocarbon source such as acetylene (CzH2). The process may comprise supplying a plasma starting gas having a flow rate of from about 4 〇〇 sccm to about 8000 SCCm, such as helium, supplying a source of a carbonium compound, such as acetylene (CzH2), from a flow rate of from about 400 seem to 8000 seem, applied from A dual-frequency 111? power of about 1 watt to about 2000 watts, maintaining the φ cavity to a pressure from about 2 Torr to about 20 Torr, and maintaining the chamber temperature from about 25 ° C to about 475 ° C . This process range provides a deposition rate for the a_C:H layer ranging from about 10 angstroms/minute to about 30,000 angstroms/minute and a conformality of from about 30% to about 100% (average of one layer deposited on the sidewalls of a feature structure) The ratio of the thickness to the average thickness of the same deposited layer on the substrate, or the upper surface. Those skilled in the art, after reading this disclosure, can calculate appropriate process parameters to produce a-C:H films having different deposition rates. In one embodiment of the deposition process, a plurality of independent amorphous 18 201026877 carbon deposits are performed to form an amorphous carbon layer. In the one aspect of the composite deposition process, the '-deposition step, as described herein, is followed by a pause, in which the plasma starting gas, the diluent gas, and/or the precursor may be reduced or absent. The state of the deposition rate circulates. Suitable electrical starting gas, diluent gas, and/or precursor may be introduced into the chamber from a flow rate of from about 1 〇〇 s to about 40,000 seem. If the plasma is used to initiate the gas, i.e., the diluent gas, the suspension step can be initiated. The bismuth deposition and pause steps can then be repeated until the desired thickness is obtained, and can be cycled from 1 to 100 times, such as from 1 to 5 cycles, for example 30 cycles, or from about 1% to about 1%. The thickness of the amorphous carbon material is between about 2, for example. /. Up to about 10% of the cycle, for example about 3 3%. Each cycle of a separate cycle can deposit an amorphous carbon material from about 1 angstrom to about 1 angstrom thick to form an amorphous carbon layer having a thickness of from about 1 angstrom to about 15 angstroms. The cyclic deposition process can be adjusted using one or more of the above process parameters. φ Alternatively, the gas can also be withdrawn and then re-introduced before the deposition step or during the pause step. The salty-multilayer deposition scheme reduces the effective film deposition rate and improves conformality. In addition, newly deposited carbon atoms can diffuse during this pause step, further improving conformality. In general, conformality increases as the number of layers of a particular amorphous carbon film layer thickness (thin individual layer thicknesses) And more repeated), and an improvement is obtained when the ratio of the deposition step time to the time of the deposition step is large (low effective deposition rate). For example, the ratio of the pause step time to the deposition step time can be from about 100:1 to about! : 1 〇〇. By adjusting the thickness of the individual layers and the ratio of the pause to the deposition time, 19 201026877 can be used to adjust the conformality of the amorphous carbon film layer to improve a specific electrical condition (precursor, carcass, flow rate, conformality). The method of the present invention, which meets the component requirements and thus provides the deposition pressure, temperature, RF power, etc. of the auxiliary chemical vapor deposition, is mainly advantageous over the conformal enhancement of other aC:H deposition processes, such as Hey? Court fight - , as shown in Figure 2. Fig. 2 is a schematic plan view showing a fine structure of a substrate having a characteristic structure 2 (an amorphous-amorphous carbon layer 2() 2 formed thereon. The amorphous carbon layer 202 shows a film deposited by the method of the present invention. ', appearance. In terms of quality, the amorphous carbon layer 202 is highly conformal and το fully covers the sidewalls and bottom of the feature structure 2〇1. In terms of quantity, the amorphous carbon layer 2〇2 can have Conformality from about 3% to about 1%, for example from about G to about 9G%, where conformality (conformality) is defined as amorphous deposited on the sidewall 2〇4 The ratio of the average thickness S of the carbon layer 2〇2 to the average thickness T of the amorphous carbon layer 2〇2 on the upper surface 205 of the substrate 200. Referring again to Fig., the non-conformal amorphous carbon layer 202 is shown To have a conformality of about 5%. An example of an amorphous carbon material deposited using the processes described herein is as follows: Comparative Example A: A comparative amorphous carbon deposition process example includes providing a helium flow rate of about 400 seem To the processing chamber, an argon flow rate of about 8 〇〇 () sccm to the processing chamber 'provides a flow rate of about 6000 seem C3H6 to the processing chamber, applying about 1250 The high frequency rf power of the watt (13 56 MHz) 'maintains the deposition temperature at about 3 〇〇, maintains the chamber pressure at about 4.5 Torr' along with a spacing of about 380 mils to reach the dense area and the open area ladder The overlay (conformality measure) produces an amorphous carbon layer having a conformality of about 2%. In a first example, by providing a helium flow rate of about 4000 sccrn 20 201026877 ^ the processing chamber provides about 2000 sccm C#2 flow rate to the treatment to 'apply about 50 watts of high frequency RF power (13.56 MHz), maintain the deposition temperature at about 400. (:, maintain the chamber pressure at about 9 Torr, together with about 3 〇〇 The mil spacing was used to deposit an amorphous carbon layer, resulting in a deposition rate of 187 angstroms per minute, and a conformality of about 96% to the open region step coverage (conformity measure) was observed to be achieved. The examples are all performed on a feature structure having an aspect ratio of about 2.1: 1. In the first example, by providing a helium flow rate of about 2000 seem to the process chamber, a C2H2 flow rate of about 200 〇seem is provided to the process® chamber. Apply about 100 watts of high frequency RF power (13.56 MHZ) to deposit temperature Maintaining at about 400 ° C, maintaining the chamber pressure at about 9 ,, along with a spacing of about 300 mils to deposit an amorphous carbon layer, yielding a deposition rate of 516 angstroms per minute, and observing a dense region of about 82 % to open area step coverage (conformality measure) about 86% conformality. Both the first example and the second example are performed on a feature structure with an aspect ratio of about 2.1:1. In a third example By providing a helium flow rate of about 4000 sccm to the processing chamber, a C2HZ flow rate of about 2000 sccm is supplied to the processing chamber, and a high frequency RF power (13 56 MHz) of about 20 watts is applied to maintain the deposition temperature at about 400. (:, maintaining the chamber pressure at about 9 Torr, along with a spacing of about 300 mils to deposit an amorphous carbon layer, resulting in a deposition rate of 64 angstroms per minute, and observing reaching a dense region of about 93% to the open area Step coverage (conformity measure) about 97% conformality. In a fourth example, by providing a helium flow rate of about 4000 sccm to the process chamber, a CzH2 flow rate of about 2000 seem is provided to the process chamber, Apply about 1 watt of high frequency RF power (13 56 MHz), maintain the deposition 21 201026877 temperature at about 40 (rc, maintain the chamber pressure at about 7 Torr, along with a spacing of about 31 mils Depositing an amorphous carbon layer. In a fifth example, an amorphous carbon layer is deposited by using a deposition cycle followed by four deposition cycles of the helium gas purification step, the deposition step providing about 4 〇〇〇 scem of germanium. The gas flow rate to the processing chamber provides a flow rate of C2H2 of about 2 〇 (10) m to the processing chamber 'applying about 1 watt of high frequency rf power (13.56 MHz), maintaining the deposition temperature at about 3 〇〇t:, the cavity The chamber pressure is maintained at approximately 9 Torr, together with a spacing of approximately 300 mils, resulting in 9 〇 A deposition rate of 9 angstroms per minute, and a dense area coverage of about 84% (conformality measure) was observed. The helium purification step was performed under the same process parameters except for no flow and no applied RF power. In a sixth example, an amorphous carbon layer is deposited using a 14-person deposition cycle followed by a helium purification step after the deposition step. The deposition step provides a low helium flow rate of about 400 seem to the processing chamber, providing about 4 〇〇seem's C2H2 flow rate to the processing chamber, applying a high frequency good power of about 1 watt (13.56 MHz)' to maintain the deposition temperature at about 3G (rc, maintaining the chamber pressure at about 7 Torr, together with The spacing of 3 mils produced a deposition rate of 9 〇 9 angstroms / knife knives, and a side wall to the top was observed. P conformality '94% sidewall to bottom conformality and 72% bottom f top °卩 conformality. The helium purification step is performed under the same process parameters except that there is no C2H2 flow and no rf power is applied. In the seventh van, you do not deposit in different power ranges. Comparison of shaped carbon layers. For two processes By providing a flow of helium gas to the processing chamber, providing about 2 〇〇〇 c and a flow rate 〇 the processing chamber 'applying about 5 watts or 2 watts of high frequency power (1) % Hz) will deposit The temperature is maintained at about 4 Torr. The chamber pressure is maintained at 22 201026877 = 9 Torr' along with a spacing of about 3 (8) mils to deposit the amorphous. =0 watt deposition process at a deposition rate of fine angstroms per minute. (4) Side-to-top conformality, and the 2G watt deposition process produces a sidewall-to-top conformality of 93-970/〇 at a deposition rate of 64 angstroms/knife. In an eighth example, the cycle is performed relative to a single step. A comparison of the amorphous carbon layer deposited by the deposition. For the two processes, by providing a helium flow rate of about 4000 sccm to the process chamber to provide a QH2 flow rate of about ο. to the process chamber, applying about 1 watt of high frequency rf power (56 MHz), The deposition temperature is maintained at about 4 Torr and the chamber pressure is maintained at about 9 Torr' along with a spacing of about 3 mils to deposit the amorphous carbon. The single-step deposition process produces 51% sidewall to top. Conformal 87/〇 sidewall-to-bottom conformality and 59% bottom-to-top conformality. The cyclic deposition step consisting of 14 cycles followed by a helium gas purification step after deposition yielded 71% sidewall to top Shape, 92% sidewall-to-bottom conformality and 77% bottom-to-top conformality. This helium purge step is performed under the same conditions except that no RF power is applied and C2H2 is not provided. In a ninth example, a comparison of the two amorphous processes with respect to the deposition of the amorphous carbon layer deposited in a single step is performed. For both processes, about 2000 is provided by providing a helium flow rate of about 4000 sccm to the process chamber. See the qH2 flow rate to the processing chamber, applying about The high frequency RF power (13.56 MHz) of 5 watts was maintained at about 4 〇〇〇c and the chamber pressure was maintained at about 9 Torr, along with a spacing of about 300 mils to deposit the amorphous carbon. The single-step deposition process uses a 25 watt RF power application and produces 56% sidewall-to-top conformality and 87% sidewall-to-top conformality of the dense structure. The first cycle of the 23rd 201026877 A cycle treatment series uses 25 times for 7 seconds, each of which is 20 angstroms above the deposition and helium cooling cycle 'to produce a dense structure of 5 5 % of the sidewalls to the top conformality and 82% of the open structure side to the top Shape; and the second series uses 10 depositions and helium cycles of 10 seconds for 15 seconds each, resulting in 54% sidewall-to-top conformality and 75% sidewalls of the open structure. For the top conformality, the first cycle of the second process series uses 25 deposition cycles of 20 seconds each for 20 seconds, resulting in 78% sidewall-to-top conformality and open structure 89 of dense structure. % of the sidewalls are conformal to the top; the second series uses 1〇 Each of the 50 angstroms and fifteen second deposition cycles produced 69% sidewall-to-top conformality and 89% sidewall-to-top conformality of the open structure, while the third series used 25 Each of the 20 angstroms of seven seconds of deposition and a 13 second stabilization step cycle yielded 55% sidewall-to-top conformality of the dense structure and 92% sidewall-to-top conformality of the open structure. 4A-41 is a schematic side view of a process for etching a layer of material using an amorphous carbon layer as described herein. A substrate material 41 is deposited on a substrate surface (not shown) to begin forming a material. Stack 40 (the substrate material may be used to form one or more materials of a semiconductor component, including a germanium substrate material, an oxide material, a polycrystalline material, or the like. A first amorphous carbon layer 42 is deposited on the base material 410, and a first anti-reflective layer material 430 is deposited on the first amorphous carbon layer 420, as shown by the 4B circle. The amorphous carbon layer can be an Advanced Exposure Pattern Film (APF) material or an amorphous carbon material as described herein available from Applied Materials, Inc. of Santa Clara, California. The first anti-reflective layer material 43G is used to control the line reflection of the light 24 201026877 during the lithography patterning process. The first anti-reflective layer material 430 may comprise cerium oxide, cerium oxynitride, cerium nitride, or a combination thereof. The antireflective layer material can be a darcTM material layer available from Applied Materials, Inc. of Santa Clara, California. A second amorphous carbon layer 440 and a second anti-reflective layer material 45A may be sequentially deposited on the first anti-reflective layer material, as shown in the figure. The first carbon-free carbon layer 440 and the second anti-reflective layer material 450 may be the same material as the deposited layer 420 and the anti-reflective coating material #43. A photoresist layer 46, such as a photoresist material, is then deposited over the second anti-reflective layer material 450, as shown in FIG. 4D. The photoresist layer ‘ is then patterned using a lithography process to produce a patterned photoresist layer 461, as shown in Fig. 4e. The first pattern 462 formed in the photoresist layer 461 first etches the second anti-reflective layer material 45 利用 by one or more etching processes, and then etches the second amorphous carbon layer 44 〇 to transfer to the second The amorphous carbon layer 440 forms a patterned second amorphous carbon layer 441, as shown in Fig. 4F. The patterned second amorphous carbon layer 441 can be used as a hard mask for the underlying material. The second anti-reflective layer material 45 can be removed by the one or more residual processes or by a separate process. The first anti-reflective layer material 430 and the patterned second amorphous carbon layer 441 A conformal amorphous carbon layer 47 is deposited thereon as shown in Fig. 4G. The conformal amorphous carbon layer can be deposited using any of the processes described herein. The conformal amorphous carbon layer 470' is patterned using an anisotropic etch process to provide sidewall amorphous carbon material 471 as shown in FIG. The presence of the sidewall amorphous carbon material 471 allows for the formation of a second pattern 472 having a reduced critical dimension and feature size compared to otherwise normalized lithography process implementations, ie, increased Figure 25 201026877 Case density. The patterned second amorphous carbon layer 441 in combination with the sidewall amorphous carbon material 471 can serve as a hard mask layer for the underlying first anti-reflective layer material 43 and the first amorphous carbon layer 420. The first anti-reflective layer material 43 is then engraved to form a patterned anti-reflective layer 431 having the second pattern 472, as shown in FIG. The patterned second amorphous carbon layer 441 and the sidewall amorphous carbon material 471 are removed during the etching process or by a subsequent process. The first amorphous carbon layer 420 is then etched to form a patterned first amorphous carbon layer 421 having a second pattern 472 to be transferred to the underlying substrate material 410. Then, the patterned first amorphous carbon layer 421 is used as a hard mask layer to etch the base material 410, as shown in FIG. 4K, and then the patterned first amorphous carbon layer 421 is removed to provide The surface of the substrate containing the patterned base material 4 of the second pattern 472 is as shown in the figure. In another embodiment, a patterned photoresist material is used in place of the patterned second amorphous carbon layer 441 for the 4F-4L pattern, thereby removing the second non-patterned pattern for the 4C-4E pattern. The shaped carbon layer 44A and a first anti-reflective layer material 450, as well as the corresponding deposition steps and etching steps, are required. 5A-5H is a schematic side view of a process for using the amorphous carbon layer described herein in a spatial mask double patterning process. A substrate material 510 is deposited on a substrate surface to begin forming a material stack 5〇〇. The substrate material may be one or more materials used to form the semiconductor component, including a germanium substrate material, an oxide material, a polysilicon material, or the like. Depositing a first amorphous carbon layer 520' on the base material 510 and forming a patterned photoresist layer 530 having a first circular pattern 532 on the first amorphous carbon layer 52, as shown in FIG. 5A. The amorphous 26 201026877 carbon layer may be an Advanced Exposure Pattern Film (APF) material that can be obtained from Applied Materials, Inc. of Santa Clara, Calif., or an amorphous carbon material as described herein. The photoresist layer 53〇1 can be patterned by a lithography process, and then the patterned photoresist layer 530 is subjected to a trimming process to narrow the width of the patterned photoresist material to form the trimmed photoresist. The first pattern 533 of the material 31 is as shown in Fig. 5B. The first amorphous carbon layer 520 is then engraved to transfer the second pattern 533 to form a patterned amorphous carbon layer 521, as shown in Figure 5c. The sidewall spacers 540 are then formed adjacent to the patterned amorphous carbon layer 521 structure. The spacer may comprise an etchable material having an etch rate different from the first amorphous carbon layer or the conformal amorphous carbon material. Suitable materials include, for example, cerium oxide, cerium oxynitride, tantalum nitride, or combinations thereof, and then conformally deposited on the sidewall spacers 54 and the patterned amorphous carbon layer 521 structure. The gap filling layer 550 of the amorphous carbon material is as shown in Fig. 5E. The conformal amorphous carbon material can be deposited using any of the processes described herein. The preferred conformal amorphous carbon material is similar in etching properties to the patterned amorphous carbon layer 521. The gap fill layer 550 is then etched back to expose the sidewall spacers 540 as shown in Figure 5F. The sidewall spacers 54 are then etched to expose the substrate material 510 to define a hard mask layer 551, as shown in Figure 5G. The base material 51 can then be patterned and etched to form a patterned substrate material 511' as shown in Figure 5H. In another process, after the patterned amorphous carbon layer 521 is formed adjacent to the sidewall spacers 54 as shown in FIG. 5D, the patterned amorphous carbon layer 521 is then removed from the substrate. Surface removal. The sidewall spacers 540 then form a pattern, as shown in Figure 5E, which can be used as a hard mask for the substrate material 510. The base material 51 is then patterned to form a patterned substrate material 511. 6A-6J is a schematic side view of a process for etching a material layer using an amorphous carbon layer as described herein, for example, using an amorphous carbon deposition process of less than 100 degrees. Depositing a substrate t 610 on a substrate surface (not shown) to begin forming a material stack 6 〇 (the substrate material can be used to form one or more material packages of the semiconductor component. An oxide material, a polycrystalline silicon material, or the like. A first amorphous carbon layer 620 is deposited on the base material 610, and an anti-reflective layer material 63 is deposited on the first amorphous carbon layer 620, such as the 66th As shown, the amorphous carbon layer can be an Advanced Exposure Pattern Film (APF) material available from Applied Materials, Inc. of Santa Clara, Calif., or an amorphous carbon material as described herein. The layer material 63 is used to control light reflection during the lithography patterning process. The anti-reflective layer material 630 may comprise cerium oxide, cerium oxynitride, cerium nitride, or a combination thereof. Is a layer of DARCTM material available from Applied Materials, Inc., Santa Clara, Calif. ® then deposits a photoresist layer 640, such as a photoresist material, on the anti-reflective layer material 630 as shown in Figure 6C. Then use one The lithography process patterning the photoresist layer ‘produces a patterned photoresist layer 641, as shown in FIG. 6. The patterned photoresist layer 641 forms a first etched pattern 642. The process and the total process described herein are utilized. A second amorphous carbon layer 65 is deposited conformally or substantially conformally on the patterned photoresist layer 641, as shown in Figure 6E. The conformal amorphous carbon layer can be utilized herein. Any of the processes described are deposited. In one example, the second amorphous carbon material is deposited using a deposition process below 100 ° C. The second and subsequent patterns are patterned and patterned; """ 28 201026877 The carbon layer 650 is formed to form a second etched pattern 652 which is smaller than the first etched pattern, for example, narrower, and the feature size is as shown in FIG. 6F. The pattern is patterned by an anisotropic etching process. A conformal second amorphous carbon layer 650 is provided to provide sidewall amorphous carbon material 651.

該側壁無定形碳材料651的存在容許第二圖案652形 成，其具有與否則可在正常情況下利用現行微影製程實 現者相比縮小的關鍵尺寸和特徵結構尺寸，即增加的圖 案密度。藉由此製程’形成在該光阻層内之特徵結構定 義的尺寸，例如關鍵尺寸，可縮減（“縮小，，），以在下方層 内提供較精細的特徵結構圖案。該圖案化光阻層641社 合該側壁無定形碳材料651可做為下方的抗反射層材； 630和該第一無定形碳層62〇的硬光罩層。 _以該侧壁無㈣碳材料651及該光阻層641形成的第 :::圖案652係利用一或多個蝕刻製程首先蝕刻該抗 反射層材料630’如第6G圖般1錢刻該卜益定形 碳層㈣，如第6H圖般’來轉移至該第一無定形碳層 ，而形成-圖案化的第一無定形碳層621。該 =第一無㈣碳層621可做為下方基底材料㈣的硬光 :二：反射層材料631可在钱刻該下方材料之前利用 、一或多個蝕刻製程或利用-分開的製程移除。 =刻該第一無定形碳層62〇以形成具有欲轉移至 無K妯材料610的第二蝕刻圖帛652之圖案化的第-第' :無宕層62卜如第6H圖所示。然後利用該圖案化的 621做為硬光罩層來㈣該基底材料 第61圖所示，接著除去該圖案化的第—無定形 層以提供含有具備該第二姓刻圖案如的圖案化 29 201026877 基底材料611之基材表面，如第6J圖所示。 第7圖係在此設置在一半導體結構中的無定形唉層的 使用之概要側視圖。第7圖揭示利用在此所述製程之一 沈積的無定形碳層的使用，其係用來作為倒T形閘極7〇〇 的犧牲側壁光罩。在該基材710上沈積一通道氧化物層 720。在該通道氧化物層上沈積一摻雜的多晶矽層73〇， 並在該摻雜的多晶矽層730上沈積一高熱氧化物（HT〇) 層740〇在該高熱氧化物（HTO)740上沈積一光罩層75〇。 圖案化該光罩層750並钱刻該氧化物層740和該播雜的 ® 多晶矽層730，以形成特徵結構755。利用在此所述方法 之一沈積的無定形碳層760係沈積在該蝕刻基材表面 上，以形成所製造的特徵結構755之側壁覆蓋。 雖然前述係針對本發明實施例，但本發明之其他及進 一步實施例可在不背離其本範圍下設計出，並且其範圍 係由如下申請專利範圍界定。 【圖式簡單說明】 Φ …、 因此可以詳細暸解上述本發明之特徵結構的方式，即 對本發明更明確的描述’簡短地在前面概述過，可藉由 參考實施例來得到’其中某些在附圖中示出。但是應注 意的是，附圖僅示出本發明之一般實施例，因此不應視 為係對其範圍之限制’因為本發明可允許其他等效實施 例0 第1圖（先前技藝）係具有一特徵結構及一非共形無定 形碳層形成在其上的基材之概要剖面圖。 30 201026877 第2圓係具有一特徵結構及一無定形碳層形成在其上 的基材之概要刳面圖。 第3圖係可用來執行根據本發明實施例之無定形碳層 沈積的基材處理系統之概要示意圖。 第4A-4L圖係使用在此所述之無定形碳層來蝕刻一材 料層的製程之一實施例的概要側視圖。 第5A-5H及5E’圖係在一空間光罩雙重圖案化製程中 使用在此所述之無定形碳層的製程之一實施例的概要側 視圖。 第6A-6J圖係使用在此所述之無定形碳層來蝕刻一材 料層的製程之另一實施例的概要側視圖。 第7圖係在此設置在一半導體結構中的無定形碳層的 使用之概要侧視圖。 為促進了解，在可能時使用相同的元件符號來表示該 等圖式共有的相同元件》預期到一實施例的元件及/或 製程步驟可有利地併入其他實施例而不需特別詳述。 【主要元件符號說明】 100、200、710 基材 111、 201、755 特徵結構 112、 202、420、421、440、441、470、520、521、62〇、 621、650、760 無定形碳層 114、204 側壁 31 201026877 203 底部 205 基材上表面 300 基材處理系統 302 真空幫浦 306 電源供應器 310 控制單元 312 中央處理單元 314 支撐電路The presence of the sidewall amorphous carbon material 651 allows for the formation of a second pattern 652 that has a reduced critical dimension and feature size, i.e., increased pattern density, that would otherwise be normalized to the current lithographic process implementation. The dimensions defined by the feature structure formed in the photoresist layer, such as critical dimensions, can be reduced ("reduced,") to provide a finer pattern of features within the underlying layer. The layer 641 incorporates the sidewall amorphous carbon material 651 as a lower anti-reflective layer; 630 and a hard mask layer of the first amorphous carbon layer 62. _With the sidewall no (four) carbon material 651 and the The ::: pattern 652 formed by the photoresist layer 641 is first etched by the one or more etching processes to etch the anti-reflective layer material 630' as shown in FIG. 6G, and the carbon layer (4) is as shown in FIG. 'to transfer to the first amorphous carbon layer to form a patterned first amorphous carbon layer 621. The = first (four) carbon layer 621 can be used as the underlying substrate material (four) of hard light: two: reflective layer The material 631 can be removed prior to the engraving of the underlying material, by one or more etching processes, or by a separate process. The first amorphous carbon layer 62 is engraved to form a material having a desired transition to the K-free material 610. The patterned first-th' of the second etched pattern 652: the flawless layer 62 is as shown in Fig. 6H. Using the patterned 621 as a hard mask layer (4) the base material shown in FIG. 61, and then removing the patterned first amorphous layer to provide a patterning 29 having the second surname pattern, such as 201026877 The surface of the substrate of the base material 611 is as shown in Fig. 6J. Fig. 7 is a schematic side view showing the use of an amorphous layer in a semiconductor structure. Fig. 7 discloses the use of the process described herein. The use of a deposited amorphous carbon layer is used as a sacrificial sidewall mask for the inverted T-shaped gate 7. A channel oxide layer 720 is deposited over the substrate 710. A doped polysilicon layer 73 is deposited, and a high thermal oxide (HT) layer 740 is deposited on the doped polysilicon layer 730. A photomask layer 75 is deposited on the high thermal oxide (HTO) 740. The mask layer 750 is patterned and the oxide layer 740 and the seeded polysilicon layer 730 are patterned to form features 755. An amorphous carbon layer 760 deposited using one of the methods described herein is deposited thereon. Etching the surface of the substrate to form the fabricated features 755 The present invention is based on the embodiments of the present invention, but other and further embodiments of the present invention can be devised without departing from the scope of the invention, and the scope thereof is defined by the following patent application scope. The manner in which the above-described features of the present invention are described in detail, that is, the more descriptive description of the present invention, which has been briefly described above, can be obtained by reference to the embodiments, some of which are illustrated in the drawings. It is to be understood that the appended drawings are not intended to A schematic cross-sectional view of a feature structure and a substrate on which a non-conformal amorphous carbon layer is formed. 30 201026877 The second circular system has a characteristic structure and a schematic plan view of a substrate on which an amorphous carbon layer is formed. Figure 3 is a schematic diagram of a substrate processing system that can be used to perform amorphous carbon layer deposition in accordance with an embodiment of the present invention. 4A-4L is a schematic side view of one embodiment of a process for etching a material layer using the amorphous carbon layer described herein. 5A-5H and 5E' are schematic side views of one embodiment of a process for using the amorphous carbon layer described herein in a spatial mask double patterning process. 6A-6J are schematic side views of another embodiment of a process for etching a material layer using the amorphous carbon layer described herein. Figure 7 is a schematic side view of the use of an amorphous carbon layer disposed in a semiconductor structure. To promote the understanding, the same elements are used to denote the same elements in the drawings, and the components and/or process steps of one embodiment are contemplated to be advantageously incorporated in other embodiments without particular detail. [Main component symbol description] 100, 200, 710 substrate 111, 201, 755 characteristic structure 112, 202, 420, 421, 440, 441, 470, 520, 521, 62 〇, 621, 650, 760 amorphous carbon layer 114, 204 Sidewall 31 201026877 203 Bottom 205 Substrate Upper Surface 300 Substrate Processing System 302 Vacuum Pump 306 Power Supply 310 Control Unit 312 Central Processing Unit 314 Support Circuit

316 控制軟體 320 喷頭 325 製程腔室 330 氣體分配盤 350 基材支撐座 360 支桿 370 加熱器元件 372 溫度感應器 390 基材 392 電漿 395 基材表面 400、500、600 材料堆疊 410、411、510、511、610、611 基底材料 43 0、431、450、63 0 抗反射層材料 460、461、53 0、531、640、641 光阻層 462 > 532 ' 642 第一圖案 32 201026877 471、 651 側壁無定形碳材料 472、 533、652 第二圖案 540 侧壁間隙壁 550 縫隙填補層 551 硬光罩層 700 閘極 720 通道氧化物層 730 多晶矽層 740 高熱氧化物層 750 光罩層 33316 control software 320 nozzle 325 process chamber 330 gas distribution plate 350 substrate support 360 struts 370 heater element 372 temperature sensor 390 substrate 392 plasma 395 substrate surface 400, 500, 600 material stack 410, 411 510, 511, 610, 611 base material 43 0, 431, 450, 63 0 antireflection layer material 460, 461, 53 0, 531, 640, 641 photoresist layer 462 > 532 ' 642 first pattern 32 201026877 471 651 sidewall amorphous carbon material 472, 533, 652 second pattern 540 sidewall spacer 550 gap filling layer 551 hard mask layer 700 gate 720 channel oxide layer 730 polysilicon layer 740 high thermal oxide layer 750 mask layer 33

Claims (1)

201026877 七、申請專利範圍： 1.一種在一基材上形成一無定形碳層的方法，其至少包 含： 將一基材設置在一基材處理室内； 將碳對氮原子比大於1:2的一碳氫化合物來源通入 該處理室； 將選自由氫氣、氣氣、氬氣、氣氣、及其組合物所組 • 成的族群之一電聚起始氣體通入該處理室，並且該碳氫 化合㈣源的體積流速對該電聚起始氣體的體積流速比 為1 : 2或更大； 在該處理室内以1瓦/平方公分或更㈣RF功率、2 托耳或更高的壓力、以及約30(rc至約48(rc的溫度產生 一電漿；以及 在該基材上形成一共形無定形碳層。 ❹2.如申明專利範圍第μ所述之方法更包含在形成該 無定形碳層之後執行一淨化處理步驟。 3.如申請專利範圍第2項所述之方法，更包含重複該無 形反形成製程步驟及該淨化處理步驟的循環約2至約 50 次。 、"J 申明專利範圍第1項所述之方法’更包含將-稀釋 34 201026877 氣體通入該處理室内，連同該氫氣前驅物、該電漿起始 氣體、或兩者。 5. 如申請專利範圍第1項所述之方法，其中上述之碳氫 化合物來源的碳對氫原子比為2 : 3或更高，並包含一或 多種選自由乙炔、乙烯乙炔、笨、笨乙烯、甲苯、二甲 苯、吡啶、苯乙酮、酚、呋喃、c3H2、C5H4、氟苯、二 氟苯、四氟笨、及六氟苯所組成的族群之化合物。 W 6. 如申請專利範圍第1項所述之方法，其中上述之碳氫 化合物氣體的體積流速對該電漿起始氣體的體積流速比 係從約1:1至約1 : 2。 7. 如申請專利範圍第1項所述之方法，其中上述之rf功 率係經施加約0·01至約5瓦/平方公分。 8·如申請專利範圍第1項所述之方法，其中上述之壓力 係從約2托耳至約20托耳。 9.如申請專利範圍第1項所述之方法，其中上述之Rf功 率係由一雙頻系統提供。 10_如申請專利範圍第1項所述之方法，其中上述之無定 形碳層擁有從約30%至約100%的共形性。 35 201026877 η·-種在-處理室内處理一基材的方法其至少包含: 執行一沈積循環，包含： 及 在1基材的—表面上形成一共形無定形碳材料 使一淨化氣體流動通過該處理室；以及 重複該循環2和50次之間。201026877 VII. Patent application scope: 1. A method for forming an amorphous carbon layer on a substrate, comprising at least: placing a substrate in a substrate processing chamber; and having a carbon to nitrogen ratio greater than 1:2 a hydrocarbon source is passed into the processing chamber; an electropolymerization starting gas selected from the group consisting of hydrogen, gas, argon, gas, and combinations thereof is passed into the processing chamber, and The volumetric flow rate of the hydrocarbon (tetra) source to the electropolymerization starting gas is 1: 2 or greater; in the treatment chamber at 1 watt / square centimeter or (four) RF power, 2 Torr or higher Pressure, and about 30 (rc to about 48 (the temperature of rc produces a plasma; and a conformal amorphous carbon layer is formed on the substrate.) 2. The method of claim 5 is further included in the formation of the After the amorphous carbon layer, a purification treatment step is performed. 3. The method according to claim 2, further comprising repeating the inversion forming process step and the cycle of the purification treatment step by about 2 to about 50 times. ;J affirmed the scope of patents The method of the invention further comprises: diluting 34 201026877 gas into the processing chamber, together with the hydrogen precursor, the plasma starting gas, or both. 5. The method of claim 1, wherein the method The hydrocarbon-derived carbon to hydrogen atom ratio is 2:3 or higher, and comprises one or more selected from the group consisting of acetylene, ethylene acetylene, stupid, stupid ethylene, toluene, xylene, pyridine, acetophenone, phenol, furan a compound of the group consisting of c3H2, C5H4, fluorobenzene, difluorobenzene, tetrafluorobenzene, and hexafluorobenzene. The method of claim 1, wherein the hydrocarbon gas is The ratio of the volumetric flow rate to the plasma starting gas is from about 1:1 to about 1:2. 7. The method of claim 1, wherein the rf power is applied by about 0. 01至约5瓦/平方厘米。 8. The method of claim 1, wherein the pressure is from about 2 Torr to about 20 Torr. 9. As described in claim 1 Method, wherein the Rf power is performed by a dual frequency system The method of claim 1, wherein the amorphous carbon layer has a conformality of from about 30% to about 100%. 35 201026877 η·-species in a treatment chamber The method of at least comprising: performing a deposition cycle comprising: and forming a conformal amorphous carbon material on a surface of a substrate to flow a purge gas through the processing chamber; and repeating the cycle between 2 and 50 times . 12:如申請專利範圍第u項所述之方法其中上述之淨 化氣體包含一惰性氣體或-碳氫化合物來源氣體。 13.如申請專利範圍第11項所述之方法，其中上述之淨 化氣體可被激發成一電聚。 14.如申請專利範圍第11項所述之方法其中上述之暫 • 停步驟時間對沈積步驟時間的比例可從約1〇〇 : !至約 1 ： 100 ° 15. 如申請專利範圍第n項所述之方法，其中上述之每 一次沈積循環可沈積2%和50%之間的無定形碳層厚度。 16. 如申請專利範圍第u項所述之方法，其中上述之在 該基材的一表面上形成一共形無定形碳材料包含： 將碳對氫原子比為1:2或更高的碳氫化合物來源通 36 201026877 入該處理室； 將選自由氫氣、氦氣、氬氣、氮氣、及其組合物所組 成的族群之一電漿起始氣體通入該處理室，並且該碳氫 化合物來源的體積流速對該電漿起始氣體的體積流速比 為1 : 2或更大； 在該處理室内以5瓦/平方公分或更低的RF功率、2 托耳或更咼的壓力、以及約300°C至約48(TC的溫度產生 一電漿。 ❹ 17. 如申請專利範圍第16項所述之方法，更包含將一稀 釋氣體通入該處理室内，連同該氫氣前驅物、該電漿起 始氣體、或兩者。 18. 如申請專利範圍第16項所述之方法，其中上述之碳 氳化合物來源的碳對氫原子比為2:3或更高，並包含一 G 或多種選自由乙炔、乙烯乙炔、苯、苯乙烯、甲苯、二 甲苯、吡啶、苯乙酮、酚、呋喃、C3jj2、c5H4、氟苯、 二氟苯、四氟苯、及六氟苯所組成的族群之化合物。 19. 如申請專利範圍第16項所述之方法，其中上述之製 程包含一或多種選自由該碳氫化合物氣體的體積流速對 該電黎·起始氣體的體積流速比係從約1:1至約1:2、 施加從約0.01至约5瓦/平方公分的RF功率、該屋力 係從約2托耳至約20托耳、以及該溫度係從約3〇〇〇c至 37 201026877 約480°C所組成的族群之處理參數 疋形碳層的方法，其至少包 20.—種在一基材上形成 含： 將一基材設置在一基材處理室内； 將碳對氫原子比大於1:2沾 ^ . ^ 1 2的一碳虱化合物來源通入 該處理室；The method of claim 5, wherein the purifying gas comprises an inert gas or a hydrocarbon source gas. 13. The method of claim 11, wherein the above-mentioned purge gas is excited to form an electropolymer. 14. The method of claim 11, wherein the ratio of the temporary stop step time to the deposition step time is from about 1 〇〇: ! to about 1: 100 ° 15. as claimed in the nth item The method wherein each of the deposition cycles described above deposits an amorphous carbon layer thickness between 2% and 50%. 16. The method of claim 5, wherein the forming a conformal amorphous carbon material on a surface of the substrate comprises: a hydrocarbon having a carbon to hydrogen atom ratio of 1:2 or higher. a source of the compound is introduced into the processing chamber; a plasma starting gas selected from the group consisting of hydrogen, helium, argon, nitrogen, and combinations thereof is introduced into the processing chamber, and the hydrocarbon source The volumetric flow rate has a volumetric flow rate ratio to the plasma starting gas of 1:2 or greater; in the processing chamber, RF power of 5 watts/cm 2 or less, pressure of 2 Torr or more, and about 300 ° C to about 48 (the temperature of TC produces a plasma. ❹ 17. The method of claim 16, further comprising introducing a diluent gas into the processing chamber, together with the hydrogen precursor, the electricity The method of claim 16, wherein the carbon ruthenium compound has a carbon to hydrogen atom ratio of 2:3 or higher and contains one or more G or more Free choice of acetylene, ethylene acetylene, benzene, styrene a compound of a group consisting of toluene, xylene, pyridine, acetophenone, phenol, furan, C3jj2, c5H4, fluorobenzene, difluorobenzene, tetrafluorobenzene, and hexafluorobenzene. The method wherein the process comprises one or more volume flow rates selected from the volume flow rate of the hydrocarbon gas to the electrophoretic starting gas from about 1:1 to about 1:2, and from about 0.01 to about 5 watts/cm 2 of RF power, the house strength is from about 2 Torr to about 20 Torr, and the temperature is from about 3 〇〇〇c to 37 201026877 480 ° C. A method for treating a parameterized carbon layer, which comprises at least 20. forming a substrate comprising: placing a substrate in a substrate processing chamber; and having a carbon to hydrogen atom ratio of greater than 1:2. a source of one carbon ruthenium compound of 12 is introduced into the processing chamber; 將選自由氫氣、氦氣、氬氣、氣氣、及其組合物所組 成的族群之一電漿起始氣體通入該處理室，並且該碳氫 化合物來源的體積流速對該電漿起始氣體的體積流速比 為1.2或更大，其中該碳氫化合物來源和該電漿起始氣 體係利用設置在距離基材表面4〇〇密爾和6〇〇密爾之間 的一氣體分配器通入該處理室； 在該處理室内以1瓦/平方公分或更低的RF功率以 及約〇°C至約1 〇〇〇C之間的溫度產生一電漿；以及 在該基材上形成一共形無定形碳層。 38Introducing a plasma starting gas selected from the group consisting of hydrogen, helium, argon, gas, and combinations thereof into the processing chamber, and the volume flow rate of the hydrocarbon source is the starting point of the plasma The volumetric flow rate ratio of the gas is 1.2 or greater, wherein the hydrocarbon source and the plasma starting gas system utilize a gas distributor disposed between 4 mils and 6 mils from the surface of the substrate. Passing into the processing chamber; generating a plasma in the processing chamber at an RF power of 1 watt/cm 2 or less and a temperature between about 〇 ° C and about 1 〇〇〇 C; and forming on the substrate A conformal amorphous carbon layer. 38
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KR20110074904A (en) 2011-07-04
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US20100093187A1 (en) 2010-04-15
WO2010045153A3 (en) 2010-07-29

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